CN117144143A - Method for extracting lithium from waste lithium ion battery anode material - Google Patents
Method for extracting lithium from waste lithium ion battery anode material Download PDFInfo
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- CN117144143A CN117144143A CN202311158350.6A CN202311158350A CN117144143A CN 117144143 A CN117144143 A CN 117144143A CN 202311158350 A CN202311158350 A CN 202311158350A CN 117144143 A CN117144143 A CN 117144143A
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- lithium
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- ion battery
- lithium ion
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 84
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002699 waste material Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 239000010405 anode material Substances 0.000 title claims abstract description 21
- 239000008188 pellet Substances 0.000 claims abstract description 61
- 238000002386 leaching Methods 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 239000011593 sulfur Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 238000005453 pelletization Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 claims description 21
- 239000002893 slag Substances 0.000 claims description 20
- 239000010406 cathode material Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 38
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 abstract description 19
- 239000010941 cobalt Substances 0.000 abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052759 nickel Inorganic materials 0.000 abstract description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052748 manganese Inorganic materials 0.000 abstract description 17
- 239000011572 manganese Substances 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 150000002739 metals Chemical class 0.000 abstract description 5
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 11
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
-
- 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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (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 belongs to the technical field of resource recovery, and discloses a method for extracting lithium from a waste lithium ion battery anode material, which comprises the following steps: step S1, uniformly mixing a waste anode material, a sulfur-containing compound and a binder, and pelletizing to obtain pellets I; s2, wrapping a layer of carbon powder on the surface of the pellet I to obtain a pellet II; step S3, roasting the pellets II to obtain a sintered material; and S4, leaching the sintered material with water to obtain a lithium-rich solution. The phenomena of adhesion of materials to furnace walls, hardening and the like in the roasting process are reduced by firstly mixing ingredients and sulfur-containing compounds in the pelletizing process and then wrapping carbon powder; the separation effect of lithium and metals such as nickel, cobalt, manganese and the like is good, and the recovery rate of lithium is high.
Description
Technical Field
The invention belongs to the technical field of resource recovery, and particularly relates to recovery of waste lithium ion batteries.
Background
Along with the continuous promotion of the strategy of pure electric driving of the national new energy automobile, the development of the Chinese new energy automobile industry is rapid, and the lithium ion battery, especially the ternary lithium ion battery, has become the main stream of the new energy automobile battery due to the advantages of high energy density, long service life and the like. Along with the rapid increase of the demand of the power lithium batteries, the quantity of the retired power batteries is increased, and the power batteries contain a large quantity of recyclable high-value metals such as lithium, nickel, cobalt and the like, and belong to valuable urban mineral resources.
In recent years, recycling enterprises generally focus attention on high-valued conversion of nickel and cobalt, the recycling value of lithium is weakened, lithium is usually precipitated as a byproduct or is enriched in slag, and efficient recycling cannot be achieved. In combination with the current state of lithium resources, there is a great need to increase the importance of recycling lithium in waste lithium ion batteries.
Aiming at the recovery of lithium in the waste power battery, most recovery enterprises currently adopt a technical route of recovering nickel, cobalt and manganese firstly and then recovering lithium, namely a wet treatment process of reduction acid leaching, chemical impurity removal, extraction separation. The method can realize the efficient leaching of metal elements in the anode material, but the subsequent separation process is longer because lithium and nickel cobalt manganese are leached out simultaneously, and the concentration of lithium ions is lower, so that a certain difficulty is brought to the subsequent recovery. To change the problems of the back-end recovery of lithium, studies on the front-end part of the recovery process have been conducted.
Chinese patent document CN 114162840A discloses a method for preferentially extracting lithium from retired ternary lithium battery materials, wherein in the step (1), a certain amount of retired ternary lithium battery materials are mixed by a certain amount of ternary acid leaching residues, magnesium chloride is added, and the mixture is obtained by mixing and stirring; step (2) reducing and roasting the mixture at a certain temperature; crushing and sieving the roasting material in the step (3) to obtain a sieving material; step (4), adding screening materials and a certain amount of pure water into a carbonization kettle for size mixing, introducing carbon dioxide for carbonization reaction, and filtering and separating to obtain carbonized liquid and nickel cobalt manganese slag; step (5) heating and decomposing the carbonized liquid at a certain temperature to separate out lithium carbonate, and returning the separated mother liquid to carbonization reaction; and (6) introducing the separated lithium carbonate into a centrifugal machine for separation and purification, and drying to obtain the battery-grade lithium carbonate. However, the preferential extraction of lithium by carbothermic reduction is not thorough in transformation of lithium and low in water solubility of lithium carbonate, resulting in low recovery of lithium. Chinese patent document CN115074540a discloses a comprehensive recovery method of valuable components of waste power batteries, comprising the following steps: (1) Mixing and roasting the waste power battery raw material and sulfate to obtain calcine; (2) Leaching the calcine with water, and filtering to obtain nickel-cobalt-manganese slag and lithium-rich solution; (3) Acid leaching is carried out on the nickel-cobalt-manganese slag, and acid leaching liquid is obtained through filtration; (4) Carrying out displacement copper removal treatment on the pickle liquor, and filtering to obtain copper-removed liquor; (5) And (3) carrying out high-temperature impurity removal and optional deep impurity removal on the copper-removed liquid to obtain a nickel-cobalt-manganese-containing sulfate solution. Chinese patent document CN111206148A discloses a method for preparing ternary cathode material by recovering waste ternary lithium battery, comprising the following steps: 1) Mixing the pretreated nickel cobalt lithium manganate waste anode powder with sulfate, and roasting to obtain a roasting product; 2) Leaching the roasting product by water to obtain leaching liquid and leaching slag; the water immersion liquid contains lithium salt; 3) Reacting the water leaching slag with an acid solution and hydrogen peroxide to obtain a nickel cobalt manganese leaching solution; 4) Removing impurities from the nickel-cobalt-manganese leaching solution, extracting cobalt, manganese and nickel, and saponifying and back-extracting the obtained organic phase to obtain pure cobalt sulfate, manganese sulfate and nickel sulfate solution; 5) And coprecipitating the nickel sulfate, cobalt sulfate and manganese sulfate solution, a sodium hydroxide solution and ammonia water, mixing the obtained precursor with lithium carbonate, sintering, and screening iron to obtain the ternary positive electrode material. However, the vulcanizing roasting method has extremely high requirements on roasting equipment, materials are easy to adhere to the inner wall of a kiln in the roasting process, equipment is easy to damage, and the hardening phenomenon of the materials is serious and is not easy to treat. In addition, the impurity cations such as potassium/sodium in the sulfate such as sodium bisulfate/potassium bisulfate are excessively introduced, which affects the quality of the subsequent lithium carbonate product.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to provide a method for extracting lithium from waste lithium ion battery anode materials.
In order to achieve the above object, the present invention provides the following specific technical solutions.
A method for extracting lithium from a waste lithium ion battery positive electrode material comprises the following steps:
step S1, uniformly mixing a waste anode material, a sulfur-containing compound and a binder, and pelletizing to obtain pellets I;
s2, wrapping a layer of carbon powder on the surface of the pellet I to obtain a pellet II;
step S3, roasting the pellets II to obtain a sintered material;
and S4, leaching the sintered material with water to obtain a lithium-rich solution.
In a further preferred scheme, the waste lithium ion battery is at least one of a waste binary lithium ion battery, a waste ternary lithium ion battery and a waste quaternary lithium ion battery.
In a further preferred embodiment, the sulfur-containing compound is at least one of sulfuric acid, ammonium sulfate, and ammonium bisulfate.
Further, the amounts of the positive electrode material and the sulfur-containing compound are based on SO in the sulfur-containing compound 4 2- The ratio of the molar amount of Li to the molar amount of Li in the positive electrode material is 0.5-2.0: 1.
In a further preferred embodiment, the binder is at least one of starch and cellulose.
Further, the using amount of the binder is 5-10% of the mass of the positive electrode material.
In a further preferred scheme, the diameter of the pellet I is 5-20 mm.
In a further preferred scheme, the carbon powder is at least one of activated carbon powder, graphite powder and acid leaching carbon slag. Wherein the acid leaching carbon slag is slag obtained by acid leaching of waste lithium ion battery powder.
Further, the granularity of the carbon powder is-200 meshes.
In a further preferable scheme, the thickness of the carbon powder wrapped by the pellets II is 0.5-1.5 mm. Or limiting the dosage of the carbon powder to be 10-50% of the mass of the anode material.
In a further preferred embodiment, the roasting atmosphere is a nitrogen atmosphere or an inert gas atmosphere; the roasting temperature is 300-750 ℃; and the roasting time is 1-3 hours.
In a further preferred embodiment, the method further comprises the steps of: lithium is precipitated from the lithium-rich solution.
Further, the method also comprises a step of impurity removal before lithium precipitation.
Compared with the prior art, the invention has the following obvious beneficial effects:
(1) When the anode material is recovered, lithium is preferentially extracted, the separation effect of lithium and metals such as nickel, cobalt, manganese and the like is good, and the recovery rate of lithium is higher.
(2) The sulfur-containing compound is firstly mixed in the pelletizing process, and then the carbon powder is coated, so that the phenomena of adhesion of materials to furnace walls, hardening and the like in the roasting process are reduced.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Fig. 2 shows SEM images and photographs before and after sintering of pellets ii of example 1, (a) SEM images before sintering, (b) SEM images after sintering, and (c) photographs after sintering.
Detailed Description
The invention aims to provide a method for extracting lithium from a waste lithium ion battery anode material, which comprises the following steps:
step S1, uniformly mixing a positive electrode material, a sulfur-containing compound and a binder, and pelletizing to obtain pellets I;
s2, wrapping a layer of carbon powder on the surface of the pellet I to obtain a pellet II;
step S3, roasting the pellets II to obtain a sintered material;
and S4, leaching the sintered material with water to obtain a lithium-rich solution.
The invention innovatively adopts low-price sulfur-containing compounds and the anode material to carry out pelleting treatment, then matches with the externally-matched carbon pellets with the outer layer coated with carbon-containing substances to realize the synergy of carbon and sulfur inside and outside the pellets, strengthens the roasting reaction process, promotes the anode material to transform into soluble lithium salt, and other valuable elements exist in an insoluble low-valence oxide form. Finally, the lithium compound in the sintering material and the compound of other valuable metals can be separated by simple water immersion, and the content of nickel, cobalt, manganese and other elements in the obtained lithium-rich solution is very low and not higher than 1g/L.
In addition, the surface of the pellet I is wrapped with a layer of carbon powder, so that the phenomena of adhesion of materials to furnace walls, hardening and the like in the simple vulcanization roasting process can be greatly improved.
In the specific embodiment of the invention, the anode material can be separated from the waste lithium ion battery by adopting the existing means. For example, the waste batteries can be subjected to pretreatment such as discharging, disassembling, screening, stripping (such as stripping with an organic solvent NMP) and the like to obtain the positive electrode material.
The method provided by the invention is suitable for treating lithium cobaltate batteries, waste binary lithium ion batteries, waste ternary lithium ion batteries, waste quaternary lithium ion batteries and the like, and is more suitable for waste binary lithium ion batteries, waste ternary lithium ion batteries, waste quaternary lithium ion batteries and the like.
In some embodiments of the present invention, the sulfur-containing compound is at least one of sulfuric acid, ammonium sulfate, and ammonium bisulfate.
According to reaction equation SO 4 2- + 2Li + =Li 2 SO 4 SO in sulfur-containing Compound 4 2- Molar amount with Li in the cathode materialThe theoretical ratio of (2) is 1:2. in some embodiments of the present invention, the amounts of positive electrode material and sulfide-containing compound in the pelletizing process of step S1 are based on SO in the sulfur-containing compound 4 2- The ratio of the molar amount of Li to the molar amount of Li in the positive electrode material is 0.5-2.0: 1. Since lithium does not fully react but partially participate in the synthesis of lithium metal acid insoluble substances with other elements, etc., SO in sulfur-containing compounds has been found during the course of research 4 2- The ratio of the molar amount of Li to the molar amount of Li in the positive electrode material is 0.5-2.0: 1 can achieve the object of the present invention.
The pelletizing adhesive is not particularly limited in the present invention, as long as it can assist the agglomeration of materials. Such as bentonite, starch, etc., which are commonly used, may be used as the binder of the present invention. In some embodiments of the present invention, the binder is at least one of starch and cellulose. The starch and the cellulose are used as the binder, no impurity is introduced after roasting, and carbon in the starch and the cellulose has certain reducibility, and the roasting process is assisted, so that the separation effect of the roasted lithium and other valuable metal elements is better. Further, the using amount of the binder is 5-10% of the mass of the positive electrode material.
In some embodiments of the present invention, the diameter of the pellet i is 5 to 20mm.
In some embodiments of the present invention, the thickness of the carbon powder wrapped by the pellets ii is 0.5-1.5 mm, or the amount of the carbon powder in the pellets ii is 10-50% of the mass of the cathode material.
The diameter of the pellets II is larger than 5mm but not more than 25mm, so that the furnace charging efficiency can be ensured in the roasting process, and the roasting reaction can be more fully carried out. The thickness or the quantity of the wrapped carbon powder is in the numerical range, the obtained pellet carbon powder has uniform thickness, good wrapping property and moderate pellet strength, and the roasted material is loose and uniform and has no phenomena of material adhesion to furnace walls, hardening and the like.
In some embodiments of the present invention, the carbon powder is at least one of activated carbon powder, graphite powder, and acid leaching carbon residue. Wherein the acid leaching carbon slag is slag obtained by acid leaching of waste lithium ion battery powder. Further preferably, the granularity of the carbon powder is-200 meshes, so that the carbon powder can be further uniformly coated on the surface of the pellet.
In some embodiments of the invention, the firing atmosphere is a nitrogen atmosphere or an inert gas atmosphere. The whole roasting process mainly takes reduction as main part, and SO can be generated by adopting a roasting auxiliary agent 2 、SO 3 、CO、NH 3 And reducing the high-valence nickel cobalt manganese in the positive electrode material by reducing gas with reducibility, so as to destroy the structure of the material and prevent reoxidation. The roasting temperature is 300-750 ℃, the roasting temperature is too low, the phase transformation of lithium and nickel cobalt manganese is incomplete, the selectivity to lithium is poor, the lithium leaching rate is reduced, and the nickel cobalt manganese leaching rate is increased; when the roasting temperature is too high, other side reactions can occur to influence the leaching rate of lithium, and the energy consumption is increased. According to the roasting process, the roasting time is adaptively adjusted, and in the specific embodiment of the invention, the roasting time is 1-3 hours.
In some embodiments of the present invention, the method further comprises the steps of: lithium is precipitated from the lithium-rich solution. Further, the method also comprises a step of impurity removal before lithium precipitation. The processes of lithium precipitation and impurity removal are carried out by adopting the conventional technical means in the field.
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The following specific embodiment mainly adopts the process flow shown in fig. 1.
Example 1
The processing object is as follows: waste ternary cathode material.
The mass percentage of each main metal element in the waste ternary cathode material is shown in table 1.
TABLE 1 content of Main metallic element in waste ternary cathode Material
10kg of waste ternary cathode material is taken and added with about 3kg of concentrated sulfuric acid with the concentration of 98 percent (SO in sulfur-containing compounds during material preparation) 4 2- Molar mass n (SO) 4 2- ) The Li molar amount n (Li) =0.5:1 of the waste ternary cathode material. ) And adding 500g of starch as a pelletizing binder, and pelletizing by using a disc pelletizer to obtain pellets I, wherein the number of the pellets with the diameter of 10-12 mm in the pellets I accounts for more than 90%.
Spraying water to wet the surface of the pellet I, adding 2kg of activated carbon powder of-200 meshes into a disc pelletizer, and obtaining the pellet II after the carbon powder is completely wrapped on the surface of the pellet I. The proportion of the pellets with the diameter of 10-15 mm in the pellets II is more than 95%.
And (3) controlling the atmosphere in the rotary furnace to be nitrogen atmosphere, and roasting the pellets II in the rotary furnace at 600 ℃ for 2 hours to obtain a sintered material.
Fig. 2 is an SEM image and photograph of pellets ii before and after firing. It can be seen that the sintered material is very loose and uniform in particles after roasting, the spherical particles of the positive electrode material disappear, and hardening does not occur. In addition, after the sinter was removed from the rotary kiln, the kiln wall was observed to be free of adhering material.
Leaching the sintered material with water, wherein the solid ratio of the leaching solution is 2:1mL/g, the leaching time is 1h, and the lithium-rich solution and the leaching slag are obtained after solid-liquid separation.
The concentration of metal elements such as lithium, nickel, cobalt, manganese and the like in the lithium-rich solution was detected and analyzed, and the results are shown in table 2.
TABLE 2 concentration of metallic elements in lithium-rich solutions
Further calculations confirm that the Li leaching rate is 99.23%, and the nickel, cobalt, and manganese leaching rates are 0.04%, 0.02%, and 0.28%, respectively. The separation effect of lithium, nickel, cobalt and manganese is good.
Comparative example 1
Comparative example 1 differs from example 1 in that: and (3) the step of wrapping the pellets I by carbon powder to obtain pellets II is omitted. The method comprises the following steps:
10kg of waste ternary cathode material is taken and added with 3kg of concentrated sulfuric acid with the concentration of 98 percent (SO in sulfur-containing compounds during batching) 4 2- Molar mass n (SO) 4 2- ) The Li molar amount n (Li) =0.5:1 of the waste ternary cathode material. ) And adding 500g of starch as a pelletizing binder, and pelletizing by using a disc pelletizer to obtain pellets I, wherein the number of the pellets with the diameter of 10-12 mm in the pellets I accounts for more than 90%.
And (3) controlling the atmosphere in the rotary furnace to be nitrogen atmosphere, and roasting the pellets I in the rotary furnace at 600 ℃ for 2 hours to obtain a sintered material.
After the sintered material is taken out of the rotary furnace, the sintered material has serious hardening phenomenon and harder texture, and the material adhesion on the wall of the rotary furnace is observed.
Leaching the sintered material with water, wherein the solid ratio of the leaching solution is 2:1mL/g, the leaching time is 1h, and the lithium-rich solution and the leaching slag are obtained after solid-liquid separation.
The concentration of metal elements such as lithium, nickel, cobalt, manganese and the like in the lithium-rich solution was detected and analyzed, and the results are shown in table 3.
TABLE 3 concentration of metallic elements in lithium-rich solutions
Further calculation determines that the leaching rate of Li is 90.94%, and the leaching rates of nickel, cobalt and manganese are 2.43%, 5.19% and 10.56%, respectively, and the leaching rate of lithium reaches 90%, but the leaching rate of nickel, cobalt and manganese is partially leached at the same time, so that the effect of preferentially extracting lithium is relatively poor.
Example 2
The processing object is as follows: the waste lithium ion battery anode material comprises a binary anode material, a ternary anode material and a quaternary anode material.
The mass percentage of each main metal element in the waste positive electrode material is shown in table 4.
TABLE 4 content of Main metallic element in waste ternary cathode Material
Taking 10kg of waste positive electrode material, adding 7.6kg of ammonium sulfate (SO in sulfur-containing compounds during the material preparation) 4 2- Molar mass n (SO) 4 2- ) And the Li molar quantity n (Li) =1:1 of the waste positive electrode material. ) And then adding 1kg of cellulose as a pelletizing binder, and pelletizing by using a disc pelletizer to obtain pellets I, wherein the number of pellets with the diameter of 5-10 mm in the pellets I accounts for more than 90%.
Spraying water to wet the surface of the pellet I, adding 5kg of graphite powder with the particle size of-200 meshes into a disc pelletizer, and obtaining the pellet II after the graphite powder is completely wrapped on the surface of the pellet I. The diameter of the pellets II is in the range of 8-12 mm.
And (3) controlling the atmosphere in the rotary furnace to be argon atmosphere, and roasting the pellets II in the rotary furnace at 750 ℃ for 1h to obtain a sintered material.
After the sinter was removed from the rotary kiln, the furnace wall of the rotary kiln was observed to be unadhesive to the material.
Leaching the sintered material with water, wherein the solid ratio of the leaching solution is 2:1mL/g, the leaching time is 2h, and the lithium-rich solution and the leaching slag are obtained after solid-liquid separation.
The concentrations of metal elements such as lithium, nickel, cobalt, and manganese in the lithium-rich solution were measured and analyzed, and the results are shown in table 5.
TABLE 5 concentration of metallic elements in lithium-rich solutions
Further calculations confirm that the Li leaching rate is 99.45%, and the nickel, cobalt, and manganese leaching rates are 0.02%, 0.01%, and 0.36%, respectively. The separation effect of lithium, nickel, cobalt and manganese is good.
Example 3
The processing object is as follows: and mixing the waste ternary lithium battery electrode powder and the waste lithium cobalt oxide electrode powder.
The mass percentages of the main metal elements in the raw materials are shown in table 6.
TABLE 6 content of part of metals in waste cathode materials
10kg of a mixture of the waste ternary lithium battery electrode powder and the waste lithium cobalt oxide electrode powder is added with 12.2kg of ammonium bisulfate (SO in sulfur-containing compounds during the material preparation) 4 2- Molar mass n (SO) 4 2- ) Li molar quantity n (Li) =2:1 of the waste ternary positive electrode material. ) And adding 800g of starch as a pelletizing binder, and pelletizing by using a disc pelletizer to obtain pellets I with the diameter of 10-12 mm.
Spraying water to wet the surface of the pellet I, adding 1kg of acid leaching carbon slag with the size of-200 meshes into a disc pelletizer, and obtaining the pellet II after the acid leaching carbon slag is completely wrapped on the surface of the pellet I. The diameter of the pellets II is all 11-13 mm.
And controlling the atmosphere in the rotary furnace to be nitrogen atmosphere, and roasting the pellets II in the rotary furnace at 300 ℃ for 3 hours to obtain a sintered material.
After the sinter was removed from the rotary kiln, the furnace wall of the rotary kiln was observed to be unadhesive to the material.
Leaching the sintered material with water, wherein the solid ratio of the leaching solution is 2:1mL/g, the leaching time is 1h, and the lithium-rich solution and the leaching slag are obtained after solid-liquid separation.
The concentrations of metal elements such as lithium, nickel, cobalt, and manganese in the lithium-rich solution were measured and analyzed, and the results are shown in table 7.
TABLE 7 concentration of metallic elements in lithium-rich solutions
Further calculations confirm that the Li leaching rate is 98.85%, and the nickel, cobalt, and manganese leaching rates are 0.12%, 0.03%, and 0.14%, respectively. The separation effect of lithium, nickel, cobalt and manganese is good.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The method for extracting lithium from the anode material of the waste lithium ion battery is characterized by comprising the following steps of:
step S1, uniformly mixing a waste anode material, a sulfur-containing compound and a binder, and pelletizing to obtain pellets I;
s2, wrapping a layer of carbon powder on the surface of the pellet I to obtain a pellet II;
step S3, roasting the pellets II to obtain a sintered material;
and S4, leaching the sintered material with water to obtain a lithium-rich solution.
2. The method of extracting lithium from a positive electrode material of a waste lithium ion battery of claim 1, wherein the waste lithium ion battery is at least one of a waste binary lithium ion battery, a waste ternary lithium ion battery, and a waste quaternary lithium ion battery.
3. The method for extracting lithium from a waste lithium ion battery cathode material according to claim 1 or 2, wherein the sulfur-containing compound is at least one of sulfuric acid, ammonium sulfate and ammonium bisulfate.
4. The method for extracting lithium from a waste lithium ion battery cathode material according to claim 3, wherein the amounts of the cathode material and the sulfur-containing compound are based on SO in the sulfur-containing compound 4 2- The ratio of the molar amount of Li to the molar amount of Li in the positive electrode material is 0.5-2.0: 1.
5. The method for extracting lithium from the waste lithium ion battery cathode material according to claim 1 or 2, wherein the binder is at least one of starch and cellulose; the using amount of the binder is 5-10% of the mass of the positive electrode material.
6. The method for extracting lithium from the waste lithium ion battery cathode material according to claim 1 or 2, wherein the diameter of the pellet I is 5-20 mm.
7. The method for extracting lithium from the waste lithium ion battery anode material according to claim 1 or 2, wherein the carbon powder is at least one of activated carbon powder, graphite powder and acid leaching carbon slag; the acid leaching carbon slag is slag obtained by acid leaching of waste lithium ion battery powder; the granularity of the carbon powder is-200 meshes.
8. The method for extracting lithium from the waste lithium ion battery anode material according to claim 1 or 2, wherein the thickness of carbon powder wrapped by the pellets II is 0.5-1.5 mm; or the dosage of the carbon powder is 10-50% of the mass of the positive electrode material.
9. The method for extracting lithium from the waste lithium ion battery cathode material according to claim 1 or 2, wherein the roasting atmosphere is a nitrogen atmosphere or an inert gas atmosphere; the roasting temperature is 300-750 ℃; and the roasting time is 1-3 hours.
10. The method for extracting lithium from a waste lithium ion battery cathode material according to claim 1 or 2, further comprising the steps of: lithium is precipitated from the lithium-rich solution.
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