CN116356147A - Method for selectively and preferentially separating lithium in electrode material of lithium ion battery - Google Patents
Method for selectively and preferentially separating lithium in electrode material of lithium ion battery Download PDFInfo
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- CN116356147A CN116356147A CN202310341270.8A CN202310341270A CN116356147A CN 116356147 A CN116356147 A CN 116356147A CN 202310341270 A CN202310341270 A CN 202310341270A CN 116356147 A CN116356147 A CN 116356147A
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- lithium
- leaching
- electrode material
- sulfuric acid
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000007772 electrode material Substances 0.000 title claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 238000002386 leaching Methods 0.000 claims abstract description 101
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 239000002893 slag Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 4
- -1 transition metal salt Chemical class 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 28
- 229910017052 cobalt Inorganic materials 0.000 claims description 24
- 239000010941 cobalt Substances 0.000 claims description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 24
- 239000011572 manganese Substances 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 17
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 238000004537 pulping Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 23
- 238000011084 recovery Methods 0.000 abstract description 9
- 230000006872 improvement Effects 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000007774 positive electrode material Substances 0.000 description 10
- 239000002184 metal Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-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
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229940073644 nickel Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- 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
- C22B7/007—Wet processes by acid leaching
-
- 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
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- Engineering & Computer Science (AREA)
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- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for selectively and preferentially separating lithium from a waste lithium ion battery anode material, which reduces the loss rate of lithium and realizes the improvement of a recovery process by separating lithium from nickel cobalt manganese in advance in the selective leaching process. The method comprises the following steps: roasting the lithium ion battery electrode material to obtain a roasted electrode material; uniformly mixing and activating the roasted electrode material with a proper amount of reducing agent and water to obtain activated slurry; adding a proper amount of sulfuric acid solution into the activated slurry, stirring and mixing to selectively and preferentially leach lithium, and carrying out solid-liquid separation on the slurry after the lithium leaching reaction is finished to obtain a lithium leaching solution and lithium leaching slag; purifying and removing impurities from the lithium leaching solution to obtain lithium salt; and (3) carrying out acid leaching, purification, extraction and separation on the lithium leaching slag to obtain transition metal salt.
Description
Technical Field
The invention relates to the technical field of resource recycling, in particular to a method capable of selectively and preferentially separating lithium in an electrode material of a lithium ion battery.
Background
At present, the method for recovering valuable metals from waste lithium ion batteries generally comprises the steps of carrying out pretreatment such as discharging, disassembling, crushing, sorting and the like on the lithium ion batteries to obtain positive electrode material powder or positive and negative electrode material mixed powder containing lithium and transition metal elements, and then carrying out acid leaching, extraction, back extraction, precipitation and other processes to recover the valuable metal elements. The acid leaching process is mainly a valuable metal full leaching process, namely, valuable metals such as lithium, nickel, cobalt and manganese in the electrode material of the lithium ion battery are leached into a solution simultaneously through inorganic acid and a reducing agent.
Patent CN114717419a discloses a method for separating and recovering nickel, cobalt, manganese and lithium of waste ternary lithium batteries, which comprises the steps of adding sulfuric acid and a reducing agent into waste ternary lithium battery anode material powder for leaching, removing impurities from the obtained leaching solution, precipitating nickel with dimethylglyoxime, and extracting to further separate manganese, cobalt and lithium. The leaching process of the method leaches lithium nickel cobalt manganese simultaneously, which is not selective, so that the separation process is long, and a large amount of sodium salt is introduced in the process of extracting and separating nickel cobalt manganese, which is not beneficial to the recovery of lithium at the tail end of the process.
The leaching process of the full leaching technology has poor selectivity, and although the leaching rate of lithium is very high, more lithium is carried in the subsequent extraction and separation process of nickel, cobalt and manganese. Second, the extraction process introduces a large amount of sodium salt, resulting in lower lithium recovery and difficult control of product lithium salt purity. And the leaching solution has complex components, longer impurity removal and extraction separation processes and high valuable metal loss rate. Therefore, the disadvantage of the full leaching process for recovering valuable metals from waste lithium ion batteries limits the industrial application value.
Disclosure of Invention
Aiming at the defects of the existing valuable metal full leaching process for recycling the waste lithium ion battery, the invention provides a method for selectively and preferentially separating lithium from the positive electrode material of the waste lithium ion battery, and the lithium is separated from nickel, cobalt and manganese in advance in the selective leaching process, so that the loss rate of the lithium is reduced, and the improvement of the recycling process is realized.
The technical scheme adopted by the invention mainly comprises the following steps:
s1: and roasting the lithium ion battery electrode material to obtain the roasted electrode material.
S2: and uniformly mixing and activating the roasted electrode material with a proper amount of reducing agent and water to obtain activated slurry.
S3: and adding a proper amount of sulfuric acid solution into the activated slurry, stirring and mixing to selectively and preferentially leach lithium, and carrying out solid-liquid separation on the slurry after the lithium leaching reaction is finished to obtain a lithium leaching solution and lithium leaching slag.
S4: and purifying and removing impurities from the lithium leaching solution to obtain lithium salt.
S5: and (3) carrying out acid leaching, purification, extraction and separation on the lithium leaching slag to obtain transition metal salt.
In the technical scheme, the method is used for removing the wrappage such as organic solvent, adhesive and the like mixed in the electrode material of the lithium ion battery through roasting pretreatment. Reducing agent is added into the aqueous solution system to reduce the valence state of partial transition metal in the positive electrode material, destroy the original stable structure of the positive electrode material and realize the activation treatment. The molar ratio of sulfuric acid to lithium element in the waste is controlled, so that lithium element in the positive electrode material can be fully leached into the solution, transition metals such as nickel, cobalt and manganese are remained in the lithium leaching slag in the form of insoluble oxide and the like, so that lithium-rich lithium leaching liquid and lithium leaching slag rich in the transition metal element are obtained, and finally lithium salt and transition metal salt are respectively prepared, thereby realizing selective preferential separation of lithium in the lithium ion battery electrode material and efficient recovery of the subsequent lithium element and transition metal element.
The lithium ion battery in the step S1 is any one or a combination of a plurality of nickel cobalt lithium manganate batteries, lithium cobaltate batteries, lithium manganate batteries or nickel cobalt lithium aluminate batteries.
The temperature of the roasting treatment in the step S1 is 300-600 ℃, and the roasting atmosphere can be vacuum or gas atmosphere, such as one or a combination of at least two of air, nitrogen, argon, carbon monoxide, carbon dioxide and water vapor.
The baking treatment in step S1 is mainly used for removing organic impurities such as electrolyte and binder mixed in the electrode material to be treated, and if the electrode material to be treated is subjected to a treatment method such as washing with an organic solvent to remove the mixed organic matters, or adopts other treatment methods to remove various impurities wrapped on the surfaces of the electrode powder particles, the baking treatment in step S1 can be omitted.
The reducing agent in the step S2 comprises any one or a combination of a plurality of oxalic acid, hydroxylamine hydrochloride, sodium sulfite, sodium thiosulfate, sodium sulfide, sodium hydrosulfide, lithium sulfide, potassium sulfide, formic acid and sodium hypophosphite.
The consumption of the reducing agent in the step S2 is 0.5-2 times of the total molar quantity of nickel, cobalt and manganese in the electrode material.
And the reduction activation temperature in the step S2 is 20-100 ℃, and the reduction activation time is 0.1-24 h.
The dosage of the sulfuric acid in the step S3 is 0.4 to 0.6 time of the molar quantity of lithium in the electrode material, and the concentration of sulfate radical after the sulfuric acid solution is mixed with the activated slurry is 0.6 to 3mol/L.
The temperature of the lithium leaching reaction in the step S3 is 20-100 ℃.
And the solid-liquid ratio of the lithium leaching reaction in the step S3 is 100-1500 g/L.
The invention has the technical characteristics and effects that:
the reactivity difference of lithium, nickel, cobalt and manganese in the positive electrode oxide is larger, wherein the reactivity of lithium is highest, but the ternary positive electrode material has high crystallinity, the lithium, nickel, cobalt, manganese and oxygen are layered structures which are distributed in a layered and regular manner, the structure is compact, and the lithium oxide with high reactivity is difficult to fully contact with sulfuric acid during direct leaching, so that the selectivity is poor.
The reducing agent slurry mixing activation pretreatment adopted by the invention can reduce part of nickel, cobalt and manganese in the positive electrode material to a lower valence state, destroy the regular layered structure and the stability of the positive electrode material, so that the leaching agent is easier to permeate into the pores and defects of the material in the leaching process, and fully react with lithium to realize selective leaching of lithium.
The control of the sulfuric acid dosage in the leaching process is a key factor, sulfuric acid is added according to the metering ratio of lithium, the molar ratio H2SO4 to Li=1 to 2 is the conventional dosage, and in order to ensure the full leaching of Li, the sulfuric acid is required to be slightly excessive, but the excessive sulfuric acid can cause the improvement of the leaching rate of nickel cobalt manganese. The conventional total leaching process is generally carried out by using H2SO4 to (0.5Li+Ni+Co+Mn) =1:1, the molar ratio of lithium to nickel cobalt manganese in the positive electrode material is Li to (Ni+Co+Mn) =1:1, that is, the theoretical molar ratio of sulfuric acid to lithium used in the total leaching process is H2SO4 to Li=1.5:1, and the theoretical use amount of sulfuric acid is 3 times the use amount of the selective preferential leaching lithium in the invention, SO that the leaching rate of nickel cobalt manganese element is ensured in actual production, and the use amount of sulfuric acid is higher than the theoretical use amount. This severe excess sulfuric acid masks differences in the reactivity of lithium, nickel, cobalt and manganese leaching and is a significant cause of non-selectivity in the leaching process. At the same time, the reaction time is a non-negligible important factor affecting the selectivity.
According to the invention, a step-by-step extraction mode is adopted, and other metal ions in a lithium leaching solution are reduced by selectively leaching the lithium element in the waste lithium battery preferentially, so that the loss of lithium in the subsequent impurity removal, separation and purification processes can be effectively reduced, and nickel, cobalt and manganese elements are enriched in lithium leaching slag and can be recovered by a conventional acid leaching method. Compared with the full leaching process, the selective lithium leaching process provided by the invention has the advantages of high selectivity, high lithium recovery rate, short flow, small pollution and the like, so that the clean and efficient selective lithium extraction process is an important technical direction for recovering the waste ternary lithium battery in the future, and has high industrialization application potential.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make the technical scheme and the beneficial effects of the invention more clear and clear, specific and detailed descriptions are given below through 3 examples and 2 comparative examples.
Example 1:
in this example, a waste electrode material of a lithium nickel cobalt manganese oxide battery was used, and the composition of metal elements therein was as shown in table 1.
TABLE 1
| Metallic element | Li | Ni | CO | Mn | Fe | Al |
| Content (wt%) | 4.84％ | 18.82％ | 6.06％ | 5.94％ | 0.26％ | 1.11％ |
The method comprises the following specific steps:
(1) Roasting the waste lithium battery electrode material for 2 hours in an air atmosphere at 400 ℃ and naturally cooling.
(2) Mixing the roasted electrode material obtained in the step (1) with oxalic acid serving as a reducing agent, adding water, mixing slurry, wherein the molar ratio of oxalic acid to nickel, cobalt and manganese in the waste is 1.8:1, the water consumption is 2 times of the total mass of the electrode material and the oxalic acid, and activating the obtained slurry for 0.5h to obtain activated slurry.
(3) Adding sulfuric acid solution into the activated slurry obtained in the step (2), wherein the molar ratio of sulfuric acid to lithium in the activated slurry is 0.6:1, adjusting the solid-liquid ratio of the lithium leaching reaction to 100g/L, carrying out the preferential lithium leaching reaction at 70 ℃, leaching for 1.5h, and filtering and separating to obtain lithium leaching liquid and lithium leaching slag.
(4) Purifying the lithium leaching solution obtained in the step (3) by adjusting pH to remove impurity metal ions, filtering to obtain a purified solution and purified slag, evaporating and crystallizing the purified solution to obtain lithium sulfate, and allowing the purified slag to enter a sulfuric acid leaching process in the step (5);
(5) And (3) leaching the lithium leaching slag obtained in the step (3) and the purified slag obtained in the step (4) by sulfuric acid, adjusting pH, purifying, removing impurities and the like to obtain nickel cobalt manganese sulfate.
In this example, the lithium leaching rate in step (3) was calculated to be 97.3% by inductively coupled plasma emission spectroscopy (ICP-OES), and the leaching rates of nickel, cobalt and manganese were 0.75%, 0.38% and 1.82%, respectively. The main phases of the lithium-leaching slag in the step (3) are graphite, nickel cobalt manganese oxide and oxalate through X-ray diffraction (XRD) analysis. The purity of the lithium sulfate obtained in the step (4) is more than 99.2%, the lithium recovery rate is 97.1%, and the recovery rate of nickel cobalt manganese calculated by nickel cobalt manganese sulfate is more than 98.8%.
Example 2:
the present example uses a waste electrode material of a lithium cobaltate battery, and the metal element composition thereof is shown in table 2.
TABLE 2
| Metallic element | Li | Ni | Co | Mn | Fe |
| Content (wt%) | 5.02％ | 0.01％ | 38.95％ | 0.02％ | 0.02％ |
The method comprises the following specific steps:
(1) Roasting the waste lithium battery electrode material for 1h in a nitrogen atmosphere at 500 ℃ and naturally cooling.
(2) Mixing the electrode material obtained in the step (1) after roasting with sodium sulfide serving as a reducing agent, adding water for size mixing, wherein the molar ratio of the sodium sulfide to cobalt in the waste is 1:1, the water consumption is 2 times of the total mass of the electrode material and the sodium sulfide, and activating the obtained slurry for 2 hours to obtain activated slurry.
(3) Adding sulfuric acid solution into the activated slurry obtained in the step (2), wherein the molar ratio of sulfuric acid to lithium in the activated slurry is 0.55:1, adjusting the solid-liquid ratio of the lithium leaching reaction to 300g/L, carrying out the preferential lithium leaching reaction at 80 ℃, reacting for 3 hours, and filtering and separating to obtain lithium leaching liquid and lithium leaching slag.
(4) And (3) purifying the lithium leaching solution obtained in the step (3) by adjusting pH to remove impurity metal ions, filtering to obtain a purified solution and purified slag, adding sodium phosphate into the purified solution, precipitating and crystallizing to obtain lithium phosphate, and allowing the purified slag to enter an acid leaching process in the step (5).
(5) And (3) leaching the lithium leaching slag obtained in the step (3) and the purified slag obtained in the step (4) by sulfuric acid, adjusting pH, purifying, removing impurities, extracting and back extracting to obtain nickel-cobalt-manganese sulfate.
In the embodiment, the lithium leaching rate in the step (3) is 96.1% and the cobalt leaching rate is 1.33% through ICP-OES detection; the main phases of the lithium leaching slag in the step (3) are cobalt oxide and graphite through XRD phase analysis. The purity of the lithium phosphate obtained in the step (4) reaches more than 99.1 percent, and the recovery rate of cobalt obtained by calculating cobalt sulfate reaches more than 99 percent.
Example 3:
in this example, a waste electrode material of a lithium nickel cobalt manganese oxide battery was used, and the composition of metal elements therein was as shown in table 3.
TABLE 3 Table 3
| Metallic element | Li | Ni | Co | Mn |
| Content (wt%) | 4.53％ | 18.74％ | 6.77％ | 10.36％ |
The method comprises the following specific steps:
(1) Roasting the waste lithium battery electrode material for 4 hours at 450 ℃ under vacuum condition, and naturally cooling.
(2) Mixing the electrode material obtained in the step (1) after roasting with a reducing agent formic acid solution, adding water for size mixing, wherein the molar ratio of formic acid to nickel, cobalt and manganese in the waste is 0.6:1, the water consumption is 1 time of the total mass of the electrode material, and activating the obtained slurry for 3 hours to obtain activated slurry.
(3) Adding sulfuric acid solution into the activated slurry obtained in the step (2), wherein the molar ratio of sulfuric acid to lithium in the activated slurry is 0.52:1, adjusting the solid-liquid ratio of the lithium leaching reaction to 1000g/L, carrying out the preferential lithium leaching reaction at 95 ℃, reacting for 2 hours, and filtering and separating to obtain lithium leaching liquid and lithium leaching slag.
(4) And (3) purifying the lithium leaching solution obtained in the step (3) by adjusting pH to remove impurity metal ions, filtering to obtain a purified solution and purified slag, evaporating and crystallizing the purified solution to obtain lithium sulfate, and enabling the purified slag to enter an acid leaching process in the step (5).
(5) And (3) leaching the lithium leaching slag obtained in the step (3) and the purified slag obtained in the step (4) by sulfuric acid, adjusting pH, purifying, removing impurities, extracting and back extracting to obtain nickel-cobalt-manganese sulfate.
In the embodiment, the lithium leaching rate in the step (3) is calculated to be 98.1% through ICP-OES detection; the main phases of the lithium leaching slag in the step (3) are nickel cobalt manganese oxide and graphite through XRD phase analysis. The purity of the lithium sulfate obtained in the step (3) reaches more than 99.3 percent, and the recovery rate of nickel, cobalt and manganese obtained by calculation of nickel, cobalt and manganese sulfate reaches more than 98.5 percent.
Comparative example 1:
the waste lithium battery electrode material is the same as in example 1, and the treatment steps are as follows:
(1) Roasting the waste lithium battery electrode material for 2 hours under the air atmosphere condition at 400 ℃ and naturally cooling;
(2) Mixing the baked electrode material obtained in the step (1) with water of equal mass, stirring for 0.5h, mixing with sulfuric acid solution, wherein the molar ratio of sulfuric acid to lithium in the baked electrode material is 0.6:1, adjusting the solid-liquid ratio of lithium leaching reaction to 100g/L, carrying out leaching reaction at 70 ℃, reacting for 1.5h, and filtering and separating to obtain leaching solution and filter residues. ICP-OES analysis results show that the leaching rates of the elements are 65.25% of lithium, 34.51% of nickel, 32.17% of cobalt and 13.32% of manganese respectively. Comparative example 1 the lithium leaching rate and selectivity of example 1 were greatly improved compared to example 1.
Comparative example 2:
the waste lithium battery electrode material is the same as in example 2, and the treatment steps are as follows:
(1) The waste lithium battery electrode material is not roasted, is directly mixed with reducing agent sodium sulfide, and is added with water for size mixing, wherein the molar ratio of the sodium sulfide to cobalt in the waste material is 1:1, the water consumption is 2 times of the total mass of the electrode material and the sodium sulfide, and the obtained slurry is activated for 2 hours to obtain activated slurry.
(2) Adding sulfuric acid solution into the activated slurry obtained in the step (1), wherein the molar ratio of sulfuric acid to lithium in the activated slurry is 0.55:1, adjusting the solid-liquid ratio of the lithium leaching reaction to 300g/L, carrying out leaching reaction at 80 ℃, reacting for 3 hours, and filtering and separating to obtain leaching liquid and filter residues. The lithium leaching rate is 76.3% and the cobalt leaching rate is 14.9% through ICP-OES detection. Comparative example 2 the lithium leaching rate and selectivity of example 2 were greatly improved compared with example 2.
Claims (4)
1. A method for selectively preferentially separating lithium from an electrode material of a lithium ion battery, the method comprising the steps of:
(1) Adding a reducing agent into the pretreated electrode material, mixing, adding water, and pulping, wherein the molar ratio of the added reducing agent to the total amount of nickel, cobalt and manganese in the electrode material after roasting is (0.6-1.8): 1, a step of; activating the mixed solution, wherein the reduction activation temperature is 20-100 ℃, and the reduction activation time is 0.1-24 h, so as to obtain activated slurry;
(2) Adding sulfuric acid solution into the activated slurry, wherein the molar ratio of the added sulfuric acid to lithium in the activated slurry is (0.52-0.6): 1, adjusting the solid-liquid ratio of the lithium leaching reaction to 100-1000 g/L, carrying out the preferential lithium leaching reaction at 70-95 ℃ for 1.5-3.0 hours, and filtering and separating to obtain lithium leaching liquid and lithium leaching slag;
(3) And purifying and removing impurities from the lithium leaching solution to obtain lithium salt, and carrying out acid leaching, purification, extraction and separation on the lithium leaching slag to obtain transition metal salt.
2. The method according to claim 1, wherein the pretreatment method of step (1) comprises washing with an organic solvent to remove mixed organic impurities or roasting at a temperature of 300 to 600 ℃.
3. The method according to claim 1, wherein the reducing agent in the step (1) is used in an amount of 0.5 to 2 times the total molar amount of nickel cobalt manganese in the electrode material; in the step (2): the dosage of sulfuric acid is 0.4 to 0.6 times of the molar quantity of lithium in the electrode material; the concentration of sulfate radical is 0.6-3 mol/L after the sulfuric acid solution is mixed with the activated slurry.
4. A method according to claim 1, 2 or 3, wherein the reducing agent is one or more of oxalic acid, hydroxylamine hydrochloride, sodium sulfite, sodium thiosulfate, sodium sulfide, sodium hydrosulfide, lithium sulfide, potassium sulfide, formic acid, sodium hypophosphite.
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