CN116995327A - Method for recycling lithium from ternary positive electrode waste - Google Patents
Method for recycling lithium from ternary positive electrode waste Download PDFInfo
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- CN116995327A CN116995327A CN202310976768.1A CN202310976768A CN116995327A CN 116995327 A CN116995327 A CN 116995327A CN 202310976768 A CN202310976768 A CN 202310976768A CN 116995327 A CN116995327 A CN 116995327A
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- 239000002699 waste material Substances 0.000 title claims abstract description 134
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 76
- 238000004064 recycling Methods 0.000 title claims abstract description 29
- 238000002386 leaching Methods 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 230000001376 precipitating effect Effects 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 38
- 239000011449 brick Substances 0.000 claims description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 26
- 229910001416 lithium ion Inorganic materials 0.000 claims description 25
- 239000002893 slag Substances 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 19
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 18
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011268 mixed slurry Substances 0.000 claims description 14
- 229920002401 polyacrylamide Polymers 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 13
- 238000007873 sieving Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 9
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 24
- 238000011084 recovery Methods 0.000 abstract description 24
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 4
- 159000000002 lithium salts Chemical class 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 33
- 235000011121 sodium hydroxide Nutrition 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000002184 metal Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 239000010926 waste battery Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- -1 nickel Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- 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
- 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
- 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
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recycling lithium from ternary positive electrode waste, which is characterized in that waste ternary battery waste is taken as a raw material after being crushed and sieved, and lithium salt is prepared by crushing, mixing, removing impurities, brickmaking shaped lump materials, roasting, leaching, precipitating lithium and the like, so that the method for recycling lithium is simple in process and high in efficiency; the tunnel kiln is adopted to bake ternary anode waste, so that the productivity is high; meanwhile, inert gas is not required to protect in the roasting process, and roasting in conventional air is safe and low in cost; acid is not needed in the reaction process, the recovery rate of lithium is high, the process flow is short, the environment is protected, the economic and technical benefits are obvious, and the recovery rate of lithium is high. Reduces the environmental pollution caused by waste resources and realizes sustainable development.
Description
Technical field:
the invention relates to a method for recycling valuable metal materials from waste materials, in particular to a method for recycling lithium from waste positive electrode materials of waste batteries, which mainly comprises the step of extracting lithium from waste positive electrode materials of waste batteries.
The background technology is as follows:
with the continuous rising and development of new energy sources of lithium batteries, new energy automobiles of lithium batteries are continuously accepted in the market, and the new energy automobiles are widely popularized as an important transportation means. As an important motive power of new energy automobiles, lithium batteries are also unprecedented developed and increased, but any chemical product has the limitation of service life and annual requirements. The scrapped lithium battery can cause serious influence on the environment and society if not treated; if the ternary positive electrode waste contains a large amount of recyclable rare metal elements, the recycling of the ternary positive electrode waste has great social and economic benefits for society and enterprises.
The determination of the Chinese double-carbon target promotes the green low-carbon and efficient cyclic utilization of resources to become an important direction of future industry development. Under the rapid promotion of new energy automobiles and energy storage markets on lithium ion batteries, a large number of waste retired lithium ion batteries will be rapidly increased in the next few years. Because of the dual properties of environment and resources, the development of green low-carbon valuable metals is realized, and the recovery and the reutilization of the valuable metals are becoming the hot spot for the research of the current waste lithium ion battery recovery field.
The waste power lithium ion battery is rich in a large amount of heavy metals such as lithium, nickel, cobalt and the like, electrolyte, binder and other organic matters, and has potential threat to natural environment and human health. The waste lithium ion battery contains a large amount of valuable metal components which far exceed the content of the valuable metal of the ore in the nature. If the safe and harmless treatment of the waste lithium ion batteries can be realized, the shortage of resources in China can be relieved, the healthy development of the industry can be promoted, and the problem of environmental pollution caused by the waste batteries can be avoided. The current output of the waste power lithium battery in China is about 34GWh, and the output of the waste power lithium battery in 2025 is expected to reach 134GWh, wherein the ternary lithium ion battery accounts for more than 50 percent.
The waste lithium batteries which are eliminated in the market at present are treated, and the waste slurry is usually subjected to reduction acid leaching, namely, the waste ternary cathode material is leached by sulfuric acid and hydrogen peroxide, so that metal elements of nickel, cobalt, manganese and lithium in the waste lithium batteries are dissolved, and pure Ni, co and Mn salt solutions are obtained by using a solution extraction process after purification. The method has simple process and low recovery rate of lithium.
And the recovery method of the waste ternary lithium battery is mainly divided into pyrometallurgy, hydrometallurgy and biological metallurgy. Pyrometallurgy has strong adaptability to raw materials, rapid reaction, but high energy consumption (smelting temperature is more than 1500 ℃) and toxic gas generation. Bacteria required for biological metallurgy have high environmental requirements and long metal extraction period, and are rarely mentioned in the general industry. Hydrometallurgy is widely applied because of the advantages of mild conditions, low energy consumption, high selectivity to metal and the like, but the problems of equipment corrosion, long purification flow, complex process, secondary pollution to the environment and the like due to the need of strong acid and reducing agent in the process are solved.
For example, chinese patent CN114684872a discloses a carbon reduction roasting recovery method of ternary positive electrode waste, which combines multiple steps of carbon reduction roasting (argon protection), water leaching, acid leaching and the like, and can effectively extract, recover and reuse ternary positive electrode waste, especially valuable metals contained in ternary positive electrode waste, and simultaneously prepare spherical ternary material precursors with high purity and high quality and LiPF6 organic solution which can be directly used as raw materials of lithium ion battery electrolyte.
In addition, chinese patent CN114597526A discloses a method for extracting lithium salt from waste materials of a ternary lithium battery by reduction roasting, wherein a scrapped lithium battery is disassembled to obtain a ternary positive plate, and the ternary positive plate is crushed and screened to obtain ternary positive powder; placing the ternary anode powder into a reducing atmosphere roasting furnace for reducing roasting to obtain a roasted ternary material; placing the roasted ternary material into a ball mill for slurrying and ball milling to obtain a ball milling ternary material; transferring the ball-milled ternary material into a reaction kettle, adding water for leaching, performing solid-liquid separation to obtain a lithium-rich solution and residues, and refining and removing impurities from the lithium-rich solution to obtain a refined lithium-rich solution; introducing carbon dioxide into the refined lithium-rich solution to obtain lithium carbonate precipitate; and (3) pulping, washing, centrifugally dewatering and drying the lithium carbonate precipitate to obtain the battery-grade lithium carbonate.
According to the technical scheme disclosed by the prior art, the recovery of lithium in the ternary lithium battery anode waste material in the prior art is performed by high-temperature roasting in a reducing atmosphere or an argon protection atmosphere, so that potential safety hazards exist in the gas atmosphere, the production cost is increased, and the high production capacity is restricted for equipment requirements. Meanwhile, the ternary lithium battery anode waste contains a large amount of other rare metal elements such as nickel, cobalt, manganese and the like besides lithium elements, and the lithium is difficult to purify in the subsequent process of separating and extracting the lithium elements due to the existence of the other rare metal elements, so that the extraction rate of the lithium is seriously influenced, and the extraction cost of the lithium is further increased.
Based on the defects existing in the prior art, how to provide a method for recycling lithium from ternary positive electrode waste, which takes ternary positive electrode waste as a raw material and is fully mixed with carbon powder, other metal elements in the ternary positive electrode waste are firstly and primarily separated before extraction and roasting, then the materials containing lithium elements are subjected to conventional roasting in a tunnel kiln by adopting pressed bricks, and the process calcining cost and the production cost are reduced under the protection of a gas-free atmosphere, and then the lithium carbonate product is prepared after crushing, leaching, purifying and lithium precipitation. The method has the advantages of large production scale, high lithium recovery rate, small equipment corrosiveness, low running cost, environmental protection, no pollution and the like. And reduces the environmental pollution in the process of resource development and utilization, thereby realizing sustainable development.
The invention comprises the following steps:
the invention provides a method for recycling lithium from ternary positive electrode waste, which is characterized in that waste ternary battery waste is taken as a raw material after being crushed and sieved, and lithium salt is prepared by crushing, mixing, removing impurities, brickmaking shaped lump materials, roasting, leaching, precipitating lithium and the like, so that the method for recycling lithium is simple in process and high in efficiency; the tunnel kiln is adopted to bake ternary anode waste, so that the productivity is high; meanwhile, inert gas is not required to protect in the roasting process, and roasting in conventional air is safe and low in cost; acid is not needed in the reaction process, the recovery rate of lithium is high, the process flow is short, the environment is protected, the economic and technical benefits are obvious, and the recovery rate of lithium is high. Reduces the environmental pollution caused by waste resources and realizes sustainable development.
The invention discloses a method for recycling lithium from ternary positive electrode waste, which takes waste ternary battery waste as raw materials after crushing and sieving, and comprises the following steps:
(a) Crushing: crushing and sieving the positive electrode material disassembled and recovered by the waste ternary batteries to obtain ternary positive electrode waste fine powder;
(b) Mixing and removing impurities: fully mixing the ternary positive electrode waste fine powder and N-methyl pyrrolidone to obtain ternary positive electrode mixed slurry; mixing the ternary positive electrode mixed slurry with polyacrylamide, adding potassium sulfate, heating to perform hydrolysis reaction on the polyacrylamide, dissolving impurity ions into a separating liquid after the reaction is finished, and performing solid-liquid separation to obtain a separating liquid and solid residues;
(c) The brick blocks are prepared by fully stirring and mixing the solid slag and a mixed binder, then stirring and mixing the solid slag and carbon powder uniformly, and sending the mixture into a pressing device to press the mixture into brick blocks to bake the mixed brick blocks;
(d) Roasting: piling up the roasting mixture brick materials on a tunnel kiln car, sending the tunnel kiln car into a tunnel kiln device, roasting the tunnel kiln at high temperature, and mechanically crushing and ball milling the roasted mixture brick materials after roasting to obtain roasting and crushing fine powder;
(e) Leaching: adding water into the roasted and crushed fine powder, fully stirring and mixing the powder for leaching, and carrying out solid-liquid separation by using a belt filter device to obtain a lithium-containing solution and leaching residues;
(f) Purifying and precipitating lithium: purifying the lithium-containing solution to remove impurities, and then precipitating lithium with sodium carbonate to prepare the battery grade lithium carbonate.
The method for recycling lithium from ternary positive electrode waste comprises the following steps:
in the step (a), the lithium content in the ternary positive electrode waste fine powder is controlled to be 2.0-6.0wt%, and the ternary positive electrode waste fine powder is less than or equal to 60 meshes.
In the method for recycling lithium from ternary positive electrode waste, in the step (b), the mass ratio of the ternary positive electrode waste fine powder to the carbon powder is 1.0:0.1-3.0, and the carbon powder is less than or equal to 60 meshes.
The method for recycling lithium from ternary positive electrode waste comprises the following steps of (b) controlling the mass ratio of ternary positive electrode waste fine powder to N-methyl pyrrolidone to be 1:2.5-2.8; the mass ratio of the ternary positive electrode mixed slurry to the polyacrylamide is controlled to be 1:0.2-0.35; and the adding amount of the potassium sulfate is controlled to be 0.01-0.05 of the mass of the ternary positive electrode waste fine powder.
In the method for recycling lithium from ternary positive electrode waste, in the step (c), the mixed binder is sodium carbonate or sodium hydroxide solution, and the added amount of the sodium carbonate or sodium hydroxide solution is used for ensuring that solid slag and carbon powder can be pressed into brick shapes without scattering after being uniformly stirred and mixed.
In the step (c), the high-temperature roasting temperature is 420-1050 ℃ and the roasting time is 0.5-3.5 h.
In the step (d), the roasting and crushing fine powder is 60-200 meshes.
In the step (e), the leaching temperature is 20-90 ℃ and the leaching time is 0.5-2.0 h.
In the method for recycling lithium from ternary positive electrode waste, in the step (e), the concentration of lithium ions in leaching residues can reach less than or equal to 0.10wt%; the lithium ion concentration of the lithium-containing solution is more than or equal to 15g/L; in the step (f), the impurity removing method comprises the steps of firstly adjusting the pH value to 8-9 by alkali to remove nickel, cobalt and manganese, and then adjusting the pH value to 11-13 by sodium carbonate and sodium hydroxide to remove calcium and magnesium.
The invention discloses a method for recycling lithium from ternary positive electrode waste, which comprises the following main process flows: crushing ternary positive electrode waste, sieving, mixing and impurity removing, adding chemical agents, removing other rare metal elements, brick making block materials, roasting in a tunnel kiln, leaching, purifying, precipitating lithium, and preparing lithium salt product battery grade lithium carbonate.
The method for recycling lithium from the ternary positive electrode waste material, disclosed by the invention, takes the ternary positive electrode waste material crushed material as a raw material, adopts the process method, and has the characteristics that the ternary positive electrode waste material is roasted by a tunnel kiln, so that the capacity is high; the roasting process is carried out under the condition of no inert gas protection, and the roasting can be carried out in the conventional air, so that the roasting is safe and the cost is low; in the existing production of extracting lithium by using ternary positive electrode waste, the process method and the device for roasting by using the tunnel kiln are not adopted, and on the one hand, the ternary positive electrode waste is mainly used as a raw material, and is difficult to press and form, namely, bricks are formed, or when the ternary positive electrode waste is sent into a tunnel kiln device to be roasted after being formed, kiln collapse is extremely easy to occur, namely, due to insufficient adhesiveness of the raw material, or the reasons of controlling the content of other metal elements in the component composition of the raw material, the raw material is extremely easy to scatter under the high-temperature condition, so that the production yield and the roasting process are seriously influenced, and the production cost is greatly increased. Secondly, in the existing process of extracting lithium by taking ternary anode waste as a raw material, production is generally required to be carried out under the condition of protective gas, and the tunnel kiln has high production cost due to high fluidity. The method does not need acid or chemical reducing agent in the reaction process, and has the advantages of high lithium recovery rate, short process flow and environmental protection.
Secondly, the invention adopts a mixing and impurity removing process, and N-methyl pyrrolidone and the like are added into the ternary positive electrode waste fine powder material to be fully mixed, so as to obtain ternary positive electrode mixed slurry; mixing the ternary positive electrode mixed slurry with polyacrylamide, adding potassium sulfate, and heating for reaction to carry out hydrolysis reaction on the polyacrylamide; through the reaction process, other rare metal ions in the ternary positive electrode waste fine powder can be removed, such as nickel, co, mn metals and the like, and the rare metal ions are dissolved into a filtering solution, namely a separating solution, and then the separating solution is used for recovering the metals such as nickel, co, mn and the like by adopting the existing process. The solid slag obtained after separation in the step contains mainly lithium element, thus facilitating the subsequent recovery of lithium, greatly improving the leaching rate of lithium and further improving the recovery rate of lithium by more than 97%;
thirdly, sodium carbonate or sodium hydroxide solution is added into the process for preparing bricks, so that the adhesiveness of solid slag and carbon powder is greatly improved when the bricks are pressed after the solid slag and the carbon powder are mixed, and the ternary anode waste fine powder is sticky but not scattered when the bricks are made, so that the kiln collapse phenomenon is greatly prevented through practical use when the ternary anode waste fine powder is sent into a tunnel kiln for roasting, and the production efficiency is improved. The production cost is reduced; the leaching rate of lithium is generally above 90%, and the highest leaching rate is above 97.6%. Realizes the change of solid waste into valuable, and has great economic and social benefits.
The specific embodiment is as follows:
the present invention will be described in further detail with reference to the following embodiments. The embodiment of the invention takes the crushed powder of the ternary positive electrode waste of a certain company as the raw material, namely the ternary positive electrode waste fine powder or the ternary positive electrode waste has the same meaning; the apparatus and methods used where not described in the following manner are prior art methods and apparatus. In the following description, unless otherwise specified, the terms "parts by mass" and "mass ratio" refer to the parts by mass.
The invention provides a method for recycling lithium from ternary positive electrode waste, which takes ternary positive electrode waste as a raw material, mainly mixes the ternary positive electrode waste with carbon powder and the like fully, presses bricks to perform conventional roasting in a tunnel kiln, performs roasting under the protection of an atmosphere without protective gas, and then prepares a lithium carbonate product after crushing, leaching, purifying and lithium precipitation. Compared with the prior art, the method has the advantages of large production scale, high lithium recovery rate up to more than 97%, small equipment corrosiveness, low running cost, environmental protection, no pollution, easy operation, high efficiency and reliability.
The method for recycling lithium from ternary positive electrode waste disclosed by the invention uses waste ternary battery waste, takes the waste ternary battery waste as a raw material after crushing and sieving, and comprises the following steps:
(a) Crushing: crushing and sieving the positive electrode material recovered by disassembling the waste ternary batteries, controlling the lithium content in the ternary positive electrode waste to be 2.0-6.0wt%, and simultaneously controlling the ternary positive electrode waste fine powder to be less than or equal to 60 meshes; obtaining ternary positive electrode waste fine powder;
(b) Mixing and removing impurities: fully mixing ternary positive electrode waste fine powder and N-methyl pyrrolidone to obtain ternary positive electrode mixed slurry; mixing the ternary positive electrode mixed slurry with polyacrylamide, adding potassium sulfate or sodium sulfate, heating to hydrolyze the polyacrylamide, and performing solid-liquid separation to obtain a separation liquid and solid slag; the mass ratio of the ternary positive electrode waste fine powder to the N-methyl pyrrolidone is controlled to be 1:2.5-2.8; the mass ratio of the ternary positive electrode mixed slurry to the polyacrylamide is controlled to be 1:0.2-0.35; simultaneously controlling the adding amount of the potassium sulfate to be 0.01-0.05 of the mass of the ternary positive electrode waste fine powder material;
(c) The brick blocks are prepared by fully stirring and mixing the solid slag and a mixed binder, then stirring and mixing the solid slag and carbon powder uniformly, and sending the mixture into a pressing device to press the mixture into brick blocks to bake the mixed brick blocks; the mixed binder is sodium carbonate or sodium hydroxide solution, and the added amount of the sodium carbonate or sodium hydroxide solution is used for ensuring that solid slag and carbon powder can be pressed into brick blocks without scattering after being uniformly stirred and mixed; the mass ratio of the ternary positive electrode waste fine powder to the carbon powder is 1.0: (0.1-3.0), and the carbon powder is less than or equal to 60 meshes; the high-temperature roasting temperature is 420-1050 ℃, and the roasting time is 0.5-3.5 h;
(d) Roasting: piling up the roasting mixture brick materials on a tunnel kiln car, sending the tunnel kiln car into a tunnel kiln device, roasting the tunnel kiln at high temperature, and mechanically crushing and ball milling the roasted mixture brick materials after roasting, wherein the roasting and crushing fine powder is 60-200 meshes; obtaining roasting and crushing fine powder;
(e) Leaching: adding water into the roasted and crushed fine powder, fully stirring and mixing the mixture for leaching, and carrying out solid-liquid separation by using a belt filter device, wherein the leaching temperature is 30-90 ℃ and the leaching time is 0.5-2.0 h. The concentration of lithium ions in the leaching slag can reach less than or equal to 0.10wt%; controlling the lithium ion concentration of the lithium-containing solution to be more than or equal to 15g/L; obtaining a lithium-containing solution and leaching residues;
(f) Purifying and precipitating lithium: purifying and removing impurities from the lithium-containing solution, wherein the method comprises the steps of firstly adjusting the pH value to 8-9 by alkali to remove a small amount of residual nickel, cobalt and manganese, and then adjusting the pH value to 11-13 by sodium carbonate and sodium hydroxide to remove calcium and magnesium; and then depositing lithium by sodium carbonate to prepare the battery grade lithium carbonate.
The technical scheme is the same as the technical scheme disclosed above, and the technical scheme is not described in the related art, such as dry ball milling and wet ball milling. The other raw materials used in the present invention are commercially available. The battery grade lithium carbonate test data prepared in examples 1-3 of the method of the present invention are shown in Table 1 below.
Example 1
Crushing the positive electrode material recovered by disassembling the waste ternary positive electrode battery, sieving with a 60-mesh sieve, taking the undersize material to obtain ternary positive electrode waste fine powder less than or equal to 60 meshes, and fully mixing the ternary positive electrode waste fine powder with N-methyl pyrrolidone to obtain ternary positive electrode mixed slurry; then mixing the ternary positive electrode mixed slurry with polyacrylamide, adding potassium sulfate or sodium sulfate, heating to make the polyacrylamide undergo the process of hydrolysis reaction, after the reaction is finished, making metal ions such as Co and Mn in the ternary positive electrode waste fine powder material, namely impurity ions relative to the lithium ions of the invention, and making them be fed into separation liquor in this step so as to be convenient for removing impurity, extracting and separating lithium ions in the following procedures; impurity ions enter into a separating liquid after solid-liquid separation to obtain a separating liquid and solid slag; the obtained solid slag mainly contains metal ions mainly containing lithium, and other metal ions enter into a separation solution; the filtration is carried out by using a suction filtration or filter pressing mode, and in the impurity removal process of the step, the mass ratio of the ternary positive electrode waste fine powder to the N-methyl pyrrolidone is controlled to be 1:2.5-2.8; the mass ratio of the ternary positive electrode mixed slurry to the polyacrylamide is controlled to be 1:0.2-0.35; simultaneously controlling the adding amount of the potassium sulfate to be 0.01-0.05 of the mass of the ternary positive electrode waste fine powder material;
then adding an adhesive sodium hydroxide solution into the solid slag, wherein the sodium hydroxide solution and the like are obtained through market, for example, the concentration of the sodium hydroxide solution is below 5%, controlling the solid slag to be mixed with the sodium hydroxide solution until the solid slag is held by hands to be not scattered, obtaining a mixed material of the solid slag and the sodium hydroxide solution, and finally, placing the mixed material and 100-mesh carbon powder in a mixer according to the mass ratio of 1:1, fully mixing the mixed material and the 100-mesh carbon powder uniformly in a pressing device, and pressing the mixture into bricks to obtain baked mixture bricks; placing the brick-shaped roasting material on a tunnel kiln car device, sending the brick-shaped roasting material into the tunnel kiln device, roasting the brick-shaped roasting material in the tunnel kiln for 3.0 hours at 850 ℃, mechanically crushing and ball milling the brick-shaped roasting material to 60-200 meshes after roasting and cooling, adding water into the roasting and crushing fine powder clinker, stirring and leaching the clinker for 1.0 hour at 60 ℃, and then carrying out solid-liquid separation to obtain a lithium-containing solution and leaching slag; the leaching rate of the detected lithium is 95.8 percent, and the concentration of lithium ions in leaching slag is 0.15 percent by weight; the lithium ion concentration of the lithium-containing solution is 24.7g/L, the pH value is adjusted to 9.0 by using caustic soda flakes, then solid-liquid separation is carried out, the pH value is adjusted to 11-13 by using sodium carbonate and sodium hydroxide to remove calcium and magnesium ions, and then the sodium carbonate is used for precipitating lithium to prepare the battery grade lithium carbonate. The recovery of lithium is shown in Table 2.
Among the technical schemes disclosed in examples 2 and 3 below, the schemes and data disclosed in example 1 and the specific embodiments are the same except for the parameters disclosed below.
Example 2
Crushing the positive electrode material recovered by disassembling the waste ternary positive electrode battery, sieving with a 60-mesh sieve, taking the sieved material to obtain ternary positive electrode waste fine powder less than or equal to 60 meshes, and then placing the ternary positive electrode waste fine powder and 100 meshes of carbon powder in a mixer according to a mass ratio of 1:0.66, fully mixing and uniformly pressing the mixture to obtain a baked mixture brick; roasting the mixture bricks in a tunnel kiln at 900 ℃ for 3.0h, mechanically crushing and ball milling to 60-200 meshes after roasting and cooling, adding water into the roasting and crushing fine powder clinker, stirring and leaching for 1.0h at 60 ℃ and then carrying out solid-liquid separation to obtain a lithium-containing solution and leaching residues; the leaching rate of the detected lithium is 97.6 percent, and the concentration of lithium ions in leaching slag is 0.10 weight percent; the lithium ion concentration of the lithium-containing solution is 26.2g/L, the pH value is adjusted to 9.0 by using caustic soda flakes, then solid-liquid separation is carried out, the pH value is adjusted to 11-13 by using sodium carbonate and sodium hydroxide to remove calcium and magnesium ions, and then the sodium carbonate is used for precipitating lithium to prepare the battery grade lithium carbonate. The recovery rate of lithium in the detected raw material ternary positive electrode waste fine powder material is shown in table 2.
Example 3
Crushing the positive electrode material disassembled and recovered by the waste ternary positive electrode battery, sieving with a 60-mesh screen, taking the sieved material to obtain ternary positive electrode waste fine powder less than or equal to 60 meshes, and then placing the ternary positive electrode waste fine powder and 100 meshes of carbon powder in a mixer according to a mass ratio of 1:2, fully mixing and uniformly pressing the mixture to obtain a baked mixture brick; roasting the mixture bricks in a tunnel kiln at 500 ℃ for 2.0h, mechanically crushing and ball milling to 60-200 meshes after roasting and cooling, adding water into the roasting and crushing fine powder clinker, stirring and leaching for 2.0h at 30 ℃ and then carrying out solid-liquid separation to obtain a lithium-containing solution and leaching residues; the leaching rate of the detected lithium is 94.5 percent, and the concentration of lithium ions in leaching slag is 0.18 weight percent; the lithium ion concentration of the lithium-containing solution is 22.8g/L, the pH value is adjusted to 9.0 by using caustic soda flakes, then solid-liquid separation is carried out, the pH value is adjusted to 11-13 by using sodium carbonate and sodium hydroxide to remove calcium and magnesium ions, and then the sodium carbonate is used for precipitating lithium to prepare the battery grade lithium carbonate.
Table 1 the detection result of the main index of the battery grade lithium carbonate prepared by the method of the invention,
illustratively, the data disclosed in Table 1 above are test data for battery grade lithium carbonate products prepared in examples 1-3. Some differences between the examples of the detection data are shown in the data in the above table 1, and the average data are shown; as can be seen from table 1 above: the method of the invention uses the crushed powder of the ternary anode waste as the raw material, the various indexes of the extracted battery lithium carbonate are superior to the quality index requirements of battery grade lithium carbonate, and the recovery rate of lithium in the raw material is as high as 97.6 percent as shown in the following table 2, etc.
Table 2; table 2 shows leaching rates and recovery rates of the present invention and comparative examples
Description: the ternary positive electrode waste lithium content (%) described in table 2 refers to the lithium extraction raw material used in the present invention; the mass (kg) of the ternary positive electrode waste is compared and illustrated by 10 kg of raw materials for comparison and convenience. As can be seen from the data in Table 2 above, the recovery rate of lithium in the present invention is nearly 6% higher than that in the prior art, and the present invention has a large throughput of raw materials, i.e. industrial and large-scale production, and has high efficiency and greater economic and social benefits. The prior art scheme is difficult to realize industrialization and scale, and the methods of the following comparative examples are all carried out by the prior art method, and the raw materials used by the method are the same as those of the invention.
Comparative example 1
The raw materials used in the following comparative examples 1 to 3 are the same as those used in examples 1 to 3, but the mixed impurity removal process is not adopted, i.e., the ternary positive electrode scrap fine powder obtained in the step (a) is not subjected to other metal ion removal treatments such as Co, mn and the like; meanwhile, the roasting mode is different from that of the tunnel kiln, namely, the roasting is carried out under the condition of reducing atmosphere; meanwhile, brick pressing is not carried out; therefore, the method has small treatment capacity on raw materials, and is not beneficial to industrialized and large-scale production;
crushing the positive electrode material recovered by disassembling the waste ternary positive electrode battery, sieving with a 60-mesh sieve, taking the undersize material to obtain ternary positive electrode waste fine powder less than or equal to 60 meshes, placing the ternary positive electrode waste fine powder into a reducing atmosphere roasting furnace for reduction roasting, wherein the reducing atmosphere in the reducing roasting atmosphere is mixed gas of carbon monoxide, nitrogen and natural gas, the reducing atmosphere concentration is 60%, the roasting temperature is 600 ℃, and the roasting time of the ternary positive electrode powder in the reducing furnace is controlled to be 3 hours, so as to obtain the roasting ternary material. And placing the roasted ternary material into a ball mill for slurrying and ball milling to obtain the ball-milled ternary material with the granularity of 100 meshes. Transferring the ball-milled pulpified material to a water leaching reaction tank for water leaching reaction, controlling the liquid-solid ratio of water leaching reaction liquid to be 4:1, controlling the reaction temperature to be 60 ℃, filtering and separating leached slurry to obtain leached liquid and leached residue, and detecting that the leaching rate of lithium is 89.8%, namely that the recovery rate of lithium is less than 90%; the concentration of lithium ions in the leaching residue is 0.53wt%. The recovery rate of lithium in the detected raw material ternary positive electrode waste fine powder material reaches 89.2 percent.
Comparative example 2
Crushing the positive electrode material recovered by disassembling the waste ternary positive electrode battery, sieving with a 60-mesh screen, taking the undersize material to obtain ternary positive electrode waste fine powder less than or equal to 60 meshes, uniformly mixing the ternary positive electrode waste fine powder with carbon powder according to a mass ratio of 2:1, introducing argon into a roasting furnace for reduction roasting at a roasting temperature of 1050 ℃, and controlling the roasting time of the ternary positive electrode powder in the roasting furnace to be 2 hours to obtain the roasted ternary material. And placing the roasted ternary material into a ball mill for slurrying and ball milling to obtain the ball-milled ternary material with the granularity of 100 meshes. And transferring the ball-milled pulpified material to a water leaching reaction tank for water leaching reaction, wherein the liquid-solid ratio of the water leaching reaction liquid is controlled to be 4:1, the reaction temperature is controlled to be 60 ℃, the leached slurry is filtered and separated to obtain leaching liquid and leached residues, the leaching rate of lithium is 89.6%, and the concentration of lithium ions in the leached residues is 0.47wt%. The recovery rate of lithium in the detected raw material ternary positive electrode waste fine powder material reaches 90.2 percent.
Comparative example 3
Crushing the positive electrode material recovered by disassembling the waste ternary positive electrode battery, sieving with a 60-mesh screen, taking the undersize material to obtain ternary positive electrode waste fine powder less than or equal to 60 meshes, uniformly mixing the ternary positive electrode waste fine powder with carbon powder according to the mass ratio of 1:2, introducing argon into a roasting furnace for reduction roasting at the roasting temperature of 900 ℃, and controlling the roasting time of the ternary positive electrode powder in the roasting furnace to be 4 hours to obtain the roasted ternary material. And placing the roasted ternary material into a ball mill for slurrying and ball milling to obtain the ball-milled ternary material with the granularity of 100 meshes. And transferring the ball-milled pulpified material to a water leaching reaction tank for water leaching reaction, wherein the liquid-solid ratio of the water leaching reaction liquid is controlled to be 4:1, the reaction temperature is controlled to be 60 ℃, the leached slurry is filtered and separated to obtain a leaching solution and leached residues, the leaching rate of lithium is 88.7%, and the concentration of lithium ions in the leaching residues is 0.51wt%. The recovery rate of lithium in the detected raw material ternary positive electrode waste fine powder material reaches 88.4 percent.
By the method, the lithium extraction efficiency in the waste ternary positive electrode battery raw material is improved, the leaching rate is also high, and the prepared battery-grade lithium carbonate product meets the quality requirement.
Claims (9)
1. A method for recycling lithium from ternary positive electrode waste material, which uses waste ternary battery waste material as raw material after crushing and sieving, is characterized by comprising the following steps:
(a) Crushing: crushing and sieving the positive electrode material disassembled and recovered by the waste ternary batteries to obtain ternary positive electrode waste fine powder;
(b) Mixing and removing impurities: fully mixing the ternary positive electrode waste fine powder and N-methyl pyrrolidone to obtain ternary positive electrode mixed slurry; mixing the ternary positive electrode mixed slurry with polyacrylamide, adding potassium sulfate, heating to perform hydrolysis reaction on the polyacrylamide, dissolving impurity ions into a separating liquid after the reaction is finished, and performing solid-liquid separation to obtain a separating liquid and solid residues;
(c) The brick blocks are prepared by fully stirring and mixing the solid slag and a mixed binder, then stirring and mixing the solid slag and carbon powder uniformly, and sending the mixture into a pressing device to press the mixture into brick blocks to bake the mixed brick blocks;
(d) Roasting: piling up the roasting mixture brick materials on a tunnel kiln car, sending the tunnel kiln car into a tunnel kiln device, roasting the tunnel kiln at high temperature, and mechanically crushing and ball milling the roasted mixture brick materials after roasting to obtain roasting and crushing fine powder;
(e) Leaching: adding water into the roasted and crushed fine powder, fully stirring and mixing the powder for leaching, and carrying out solid-liquid separation by using a belt filter device to obtain a lithium-containing solution and leaching residues;
(f) Purifying and precipitating lithium: purifying the lithium-containing solution to remove impurities, and then precipitating lithium with sodium carbonate to prepare the battery grade lithium carbonate.
2. The method for recycling lithium from ternary positive electrode waste according to claim 1, characterized in that:
in the step (a), the lithium content in the ternary positive electrode waste fine powder is controlled to be 2.0-6.0wt%, and the ternary positive electrode waste fine powder is less than or equal to 60 meshes.
3. The method for recycling lithium from ternary positive electrode waste according to claim 1, characterized in that: in the step (b), the mass ratio of the ternary positive electrode waste fine powder to the carbon powder is 1.0: (0.1-3.0), and the carbon powder is less than or equal to 60 meshes.
4. The method for recycling lithium from ternary positive electrode waste according to claim 1, characterized in that: and (b) controlling the mass ratio of the ternary positive electrode waste fine powder to the N-methyl pyrrolidone to be 1:2.5-2.8; the mass ratio of the ternary positive electrode mixed slurry to the polyacrylamide is controlled to be 1:0.2-0.35; and the adding amount of the potassium sulfate is controlled to be 0.01-0.05 of the mass of the ternary positive electrode waste fine powder.
5. The method for recycling lithium from ternary positive electrode waste according to claim 1, characterized in that: and (c) the mixed binder is sodium carbonate or sodium hydroxide solution, and the added amount of the sodium carbonate or sodium hydroxide solution is used for ensuring that the solid slag and the carbon powder can be pressed into brick shapes without scattering after being uniformly stirred and mixed.
6. The method for recycling lithium from ternary positive electrode waste according to claim 1, characterized in that: in the step (c), the high-temperature roasting temperature is 420-1050 ℃ and the roasting time is 0.5-3.5 h.
7. The method for recycling lithium from ternary positive electrode waste according to claim 1, characterized in that: in the step (d), the roasting and crushing fine powder is 60-200 meshes.
8. The method for recycling lithium from ternary positive electrode waste according to claim 1, characterized in that: in the step (e), the leaching temperature is 20-90 ℃ and the leaching time is 0.5-2.0 h.
9. The method for recycling lithium from ternary positive electrode waste according to claim 1, wherein the method comprises the steps of: in the step (e), the concentration of lithium ions in the leaching slag can reach less than or equal to 0.10wt%; the lithium ion concentration of the lithium-containing solution is more than or equal to 15g/L; in the step (f), the impurity removing method comprises the steps of firstly adjusting the pH value to 8-9 by alkali to remove nickel, cobalt and manganese, and then adjusting the pH value to 11-13 by sodium carbonate and sodium hydroxide to remove calcium and magnesium.
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| CN117904453B (en) * | 2024-03-18 | 2024-05-28 | 赣州赛可韦尔科技有限公司 | Method for recovering and selectively extracting lithium from lithium battery and application thereof |
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