CN114231744A - Method for recovering lithium, cobalt, nickel and manganese from waste lithium batteries - Google Patents
Method for recovering lithium, cobalt, nickel and manganese from waste lithium batteries Download PDFInfo
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- CN114231744A CN114231744A CN202111386492.9A CN202111386492A CN114231744A CN 114231744 A CN114231744 A CN 114231744A CN 202111386492 A CN202111386492 A CN 202111386492A CN 114231744 A CN114231744 A CN 114231744A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 30
- 239000010941 cobalt Substances 0.000 title claims abstract description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 30
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 28
- 239000011572 manganese Substances 0.000 title claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 claims abstract description 21
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 17
- 239000002893 slag Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims 1
- 235000003891 ferrous sulphate Nutrition 0.000 claims 1
- 239000011790 ferrous sulphate Substances 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims 1
- 239000012265 solid product Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000002386 leaching Methods 0.000 abstract description 24
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 238000011084 recovery Methods 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 13
- 150000002739 metals Chemical class 0.000 abstract description 10
- 239000010405 anode material Substances 0.000 abstract description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- -1 ammonium ions Chemical class 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 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
- 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
- 238000004137 mechanical activation Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for recovering lithium, cobalt, nickel and manganese from waste lithium batteries, which comprises the following steps: (1) discharging and disassembling the waste lithium battery to obtain a positive electrode material; (2) uniformly mixing the positive electrode material obtained in the first step with ferric sulfate according to a certain mass ratio, and roasting at a certain temperature for a certain time to obtain roasted slag; (3) leaching the roasting slag obtained in the second step by using deionized water, and then carrying out suction filtration to separate solid from liquid to obtain leachate containing lithium, cobalt, nickel and manganese and rich Fe2O3The leached residue. According to the invention, the valuable metals of lithium, cobalt, nickel and manganese are efficiently recovered by mixing and roasting the waste lithium battery anode material and ferric sulfate salt and performing hydrothermal leaching, wherein the recovery rate of lithium is up to more than 97% at most, and the recovery rates of nickel, cobalt and manganese exceed 90%. Meanwhile, no waste liquid is generated, the operation is simple, the cost is low, the separation is easy, the method is safe and environment-friendly, and the method is a green and environment-friendly recovery method.
Description
Technical Field
The invention belongs to the field of resource recycling and hydrometallurgy, and mainly relates to a method for recovering lithium, cobalt, nickel and manganese from waste lithium batteries.
Background
With the rapid development of new energy automobiles, the demand and the capacity of lithium ion batteries are remarkably improved. The lithium ion battery is expected to have a machine loading capacity of 406GWh in 2025, wherein the machine loading capacity of the ternary battery reaches 247.5GWh, and the machine loading capacity of the lithium iron phosphate battery reaches 158.5 GWh. The service life of the lithium ion battery is generally 3 years, and after the service life of the lithium ion battery is finished, a large amount of waste lithium ion batteries can be generated, so that serious environmental pollution and resource waste can be caused.
In the field of electric automobiles, the loading capacity of ternary lithium ion batteries is huge, and the ternary waste lithium ion batteries contain metal resources such as lithium, nickel, cobalt, manganese, copper and the like. However, the nickel and cobalt resources are scarce in China and mainly depend on foreign import. In addition, although the lithium resources in China are rich and mainly distributed in plateau areas and salt lake areas, the exploitation difficulty is high, and the extraction cost is high. Therefore, under the condition of increasing shortage of production resources, the recovery treatment and resource utilization of valuable metals in the waste ternary lithium ion battery have very wide application prospects and economic values.
At present, the recovery method of waste ternary lithium ion batteries is mainly wet recovery, namely, the waste batteries are subjected to the working procedures of discharging, disassembling, crushing, sorting and the like, the screened anode powder is dissolved by using an inorganic compound reducing agent (for example, patent CN111261967), and then lithium, nickel, cobalt and manganese valuable metals in the solution are recovered by adopting the modes of a chemical precipitation method, a solvent extraction method, an ion exchange method, an electrochemical method and the like, however, the use of inorganic acid and the reducing agent causes the acid concentration of a leaching solution to be too high, which is not beneficial to subsequent recovery, and the price of the reducing agent is high, and the process is not very economic. Patent CN106785167A proposes a method for recovering lithium in waste ternary lithium batteries by further water leaching through mechanical activation, the recovery rate of lithium is more than 75%, however, the extraction rate of lithium in the process is low, and the extraction rate of other valuable metals such as nickel, cobalt and manganese is low; in patent CN106505270A, an ammonium sulfate roasting process is adopted to roast the waste lithium battery positive plate and ammonium sulfate at 550-650 ℃, so that lithium and cobalt in the waste lithium battery positive plate are extracted, the recovery rate reaches over 90%, the process can obtain a high extraction rate, but the existence of ammonium ions in the leachate causes certain difficulty in subsequent metal classification and recovery, and the recycling of the ammonium sulfate causes high energy consumption; patent CN107586960A adopts the process of sodium salt roasting and further acid leaching to extract valuable metals in waste lithium batteries, mainly adopts sodium chloride to roast with anode materials at 650-850 ℃, further adopts hydrochloric acid leaching, the extraction rate of each valuable metal element reaches more than 95%, the process can also obtain higher extraction rate, but chlorine gas can be generated in the sodium salt roasting process to pollute the environment, and the corrosion resistance requirements of equipment for the sodium salt roasting or the hydrochloric acid leaching are higher, and the acid concentration and the sodium ion concentration in the leachate are unfavorable for the recovery of the subsequent valuable metals. In summary, the existing recovery technology of waste ternary lithium batteries still has the problems of complex process and difficult treatment of leachate and the like for recovering valuable metals of lithium, nickel, cobalt and manganese. Therefore, it is urgently needed to develop a method for simply and efficiently recovering lithium, cobalt, nickel and manganese from waste lithium batteries to realize efficient recovery and resource utilization of valuable metals in the waste lithium batteries.
Disclosure of Invention
The invention provides a method for simply and efficiently recovering lithium, cobalt, nickel and manganese from waste lithium batteries, aiming at the problem of recycling valuable metals of the waste lithium batteries.
The invention discloses a method for recovering lithium, cobalt, nickel and manganese from waste lithium batteries, which takes the waste lithium batteries as raw materials and ferric sulfate as an auxiliary agent, and comprises the following process steps in sequence:
1. pretreatment of waste lithium battery
Putting the waste lithium battery into a saturated sodium chloride solution for 24 hours, fully discharging, drying in an oven at 80 ℃ for 12 hours, and disassembling to obtain a positive electrode material;
2. baking of positive electrode material
Uniformly mixing the positive electrode material with ferric sulfate, and controlling the mass ratio of the positive electrode material to the ferric sulfate to be 1: 1-8; roasting the mixed material at 500-800 ℃ for 30-240 min to obtain roasting slag;
3. leaching of roasting slag
Leaching the roasting slag obtained in the step 2 with deionized water at 25-100 ℃, wherein the leaching time is 30-180 min, the liquid-solid mass ratio is 1-8: 1, and performing solid-liquid separation on the leaching slurry to obtain leaching solution containing lithium, cobalt, nickel and manganese and filter residue (the main component is Fe)2O3)；
Compared with the prior art, the invention has the following advantages: (1) the process adopts the waste lithium battery as the raw material, reduces the environmental pollution and saves the production cost; (2) the process efficiently realizes the comprehensive recovery of the valuable metals lithium, cobalt, nickel and manganese; the process adopts ferric sulfate salt as an auxiliary agent, and iron ions enter leaching residues in the form of ferric oxide after roasting, so that the iron ions can be efficiently separated from valuable metal elements in the leaching solution, and the subsequent treatment of the leaching solution is facilitated; (4) the invention has simple process, convenient operation, low production cost, safety and stability.
Drawings
FIG. 1 is an abstract attached drawing and is a process flow chart of the invention
Detailed Description
The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.
Example one
(1) Putting the waste lithium battery into a saturated sodium chloride solution for 24 hours, fully discharging, drying in an oven at 80 ℃ for 12 hours, and disassembling to obtain a positive electrode material;
(2) uniformly mixing the positive electrode material with ferric sulfate salt, wherein the mass ratio of the positive electrode material to the ferric sulfate salt is 1: 1; roasting the mixed material at 800 ℃ for 30min to obtain roasted slag;
(3) leaching the roasting residue obtained in the step 2 with deionized water at 25 ℃ for 180min, wherein the liquid-solid mass ratio is 8:1, and performing solid-liquid separation to obtain leaching solution containing lithium, nickel, cobalt and manganese and filter residue; wherein the extraction rates of lithium, nickel, cobalt and manganese are respectively 96.2%, 94.1%, 93.4% and 93.1%.
Example two
(1) Putting the waste lithium battery into a saturated sodium chloride solution for 24 hours, fully discharging, drying in an oven at 80 ℃ for 12 hours, and disassembling to obtain a positive electrode material;
(2) uniformly mixing the positive electrode material with ferric sulfate salt, wherein the mass ratio of the positive electrode material to the ferric sulfate salt is 1: 3; roasting the mixed material at 750 ℃ for 100min to obtain roasted slag;
(3) leaching the roasting residue obtained in the step 2 with deionized water at 50 ℃ for 135min, wherein the liquid-solid mass ratio is 5:1, and performing solid-liquid separation to obtain leaching solution containing lithium, nickel, cobalt and manganese and filter residue; wherein the extraction rates of the lithium, nickel, cobalt and manganese are respectively 97.4%, 94.3%, 92.4% and 92.4%.
EXAMPLE III
(1) Putting the waste lithium battery into a saturated sodium chloride solution for 24 hours, fully discharging, drying in an oven at 80 ℃ for 12 hours, and disassembling to obtain a positive electrode material;
(2) uniformly mixing the positive electrode material with ferric sulfate salt, wherein the mass ratio of the positive electrode material to the ferric sulfate salt is 1: 5; roasting the mixed material at 600 ℃ for 170min to obtain roasted slag;
(3) leaching the roasting residue obtained in the step 2 with deionized water at 75 ℃ for 90min, wherein the liquid-solid mass ratio is 3:1, and performing solid-liquid separation to obtain leaching solution containing lithium, nickel, cobalt and manganese and filter residue; wherein the extraction rates of the lithium, nickel, cobalt and manganese are respectively 97.6%, 94.6%, 94.2% and 94.1%.
Example four
(1) Putting the waste lithium battery into a saturated sodium chloride solution for 24 hours, fully discharging, drying in an oven at 80 ℃ for 12 hours, and disassembling to obtain a positive electrode material;
(2) uniformly mixing the positive electrode material with ferric sulfate salt, wherein the mass ratio of the positive electrode material to the ferric sulfate salt is 1: 8; roasting the mixed material at 500 ℃ for 240min to obtain roasted slag;
(3) leaching the roasting residue obtained in the step 2 with deionized water at 100 ℃, wherein the leaching time is 30min, and the liquid-solid mass ratio is 1:1, and performing solid-liquid separation to obtain leaching solution containing lithium, nickel, cobalt and manganese and filter residue; wherein the extraction rates of lithium, nickel, cobalt and manganese are respectively 95.2%, 93.1%, 93.4% and 91.8%.
Claims (5)
1. A method for recovering lithium, cobalt, nickel and manganese from waste lithium batteries is characterized by comprising the following steps:
step 1: putting the waste lithium battery into a saturated sodium chloride solution for 24 hours, fully discharging, drying in an oven at 80 ℃ for 12 hours, and disassembling to obtain a positive electrode material;
step 2: uniformly mixing the positive electrode material and ferric sulfate salt according to a certain mass ratio, and roasting at a certain temperature to obtain roasting slag;
and step 3: and (3) magnetically stirring the roasting slag obtained in the step (2) with deionized water at a certain temperature for a certain time, and performing suction filtration on the leachate to realize solid-liquid separation to obtain leachate containing lithium, cobalt, nickel and manganese and iron-containing filter residue.
2. The method for recovering lithium nickel cobalt manganese from waste lithium batteries according to claim 1, wherein the iron sulfate salt in step 2 comprises one or more of ferric sulfate and ferrous sulfate.
3. The method for recovering lithium, nickel, and manganese from waste lithium batteries according to claim 1, wherein the mass ratio of the positive electrode material in the step 2 to the ferric sulfate salt is 1: 1-8.
4. The method for recovering lithium, cobalt, nickel and manganese from waste lithium batteries according to claim 1, wherein the roasting temperature of the material mixing and roasting in the step 2 is 500-800 ℃, and the roasting time is 30-240 min.
5. The method for recovering lithium, cobalt, nickel and manganese from waste lithium batteries according to claim 1, wherein the solid product in the step 3 is leached at a water immersion temperature of 25-100 ℃ for 30-180 min, and the liquid-solid mass ratio is 1-8: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115725866A (en) * | 2022-11-21 | 2023-03-03 | 北京工业大学 | Method for preferentially recovering manganese from waste lithium-rich manganese-based positive electrode material |
| US12119464B2 (en) | 2022-11-21 | 2024-10-15 | Beijing University Of Technology | Method for preferentially recovering manganese from waste lithium-rich manganese-based cathode material |
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| CN115725866A (en) * | 2022-11-21 | 2023-03-03 | 北京工业大学 | Method for preferentially recovering manganese from waste lithium-rich manganese-based positive electrode material |
| CN115725866B (en) * | 2022-11-21 | 2023-12-22 | 北京工业大学 | Method for preferentially recycling manganese from waste lithium-rich manganese-based positive electrode material |
| US12119464B2 (en) | 2022-11-21 | 2024-10-15 | Beijing University Of Technology | Method for preferentially recovering manganese from waste lithium-rich manganese-based cathode material |
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