CN111960480A - Method for preparing nickel-cobalt-manganese ternary material by using waste lithium ion battery - Google Patents
Method for preparing nickel-cobalt-manganese ternary material by using waste lithium ion battery Download PDFInfo
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- CN111960480A CN111960480A CN202010885634.5A CN202010885634A CN111960480A CN 111960480 A CN111960480 A CN 111960480A CN 202010885634 A CN202010885634 A CN 202010885634A CN 111960480 A CN111960480 A CN 111960480A
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- cobalt
- nickel
- lithium ion
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- 239000002699 waste material Substances 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 35
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 127
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000002243 precursor Substances 0.000 claims abstract description 44
- 239000002244 precipitate Substances 0.000 claims abstract description 38
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000013543 active substance Substances 0.000 claims abstract description 33
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 30
- 239000012266 salt solution Substances 0.000 claims abstract description 29
- 150000007524 organic acids Chemical class 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- 230000007935 neutral effect Effects 0.000 claims abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 13
- 230000010355 oscillation Effects 0.000 claims abstract description 13
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 10
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 10
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000007774 positive electrode material Substances 0.000 claims abstract description 9
- 238000010344 co-firing Methods 0.000 claims abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 51
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 33
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 21
- 239000012498 ultrapure water Substances 0.000 claims description 21
- 235000006408 oxalic acid Nutrition 0.000 claims description 17
- 239000005711 Benzoic acid Substances 0.000 claims description 13
- 235000010233 benzoic acid Nutrition 0.000 claims description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- 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 11
- 235000019253 formic acid Nutrition 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 235000011054 acetic acid Nutrition 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 abstract description 26
- 239000011888 foil Substances 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000001914 filtration Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000002386 leaching Methods 0.000 description 11
- 239000011572 manganese Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 229940053662 nickel sulfate Drugs 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 7
- 238000000975 co-precipitation Methods 0.000 description 7
- 230000001502 supplementing effect Effects 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000010668 complexation reaction Methods 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for preparing a nickel-cobalt-manganese ternary material by utilizing a waste lithium ion battery, which comprises the following steps of: discharging the waste lithium ion battery, and detaching a positive plate; placing the positive plate in an organic solvent for ultrasonic oscillation, and separating a positive active substance; dissolving the washed and dried positive active substance with an organic acid solution to form a metal ion solution; adding a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution into the metal ion solution to obtain a salt solution; adding a sodium hydroxide solution and ammonia water into the salt solution, adjusting the pH value of the mixed solution to be alkaline, generating a ternary precursor precipitate, and separating and drying the ternary precursor precipitate; adjusting the residual salt solution to be neutral, adding a sodium carbonate solution into the neutral salt solution to generate lithium carbonate precipitate, and separating and drying the lithium carbonate precipitate; and co-firing the ternary precursor precipitate and the lithium carbonate precipitate to obtain the lithium carbonate. The method can effectively solve the problems that the positive active material and the aluminum foil are difficult to separate and secondary waste liquid is easy to generate in the existing recovery method.
Description
Technical Field
The invention relates to the technical field of recovery of nickel-cobalt-manganese ternary materials in lithium ion batteries, in particular to a method for recovering nickel-cobalt-manganese ternary materials in waste lithium ion batteries.
Background
The lithium ion battery has the advantages of high energy density, high working voltage, high safety, long cycle life and the like, and is widely applied to the fields of mobile phones, notebook computers, energy storage base stations, vehicles and the like. With the updating of electronic products, the number of scrapped lithium ion batteries is increasing. On one hand, the direct discarding of the waste lithium ion battery causes great environmental pollution, and heavy metals enter human bodies through the way of atmosphere, soil, water source and the like, so that the heavy metals cause damage to human health and even cause cancer. On the other hand, the recovery of nickel, cobalt and manganese metal elements in the waste lithium ion battery can generate considerable economic benefit, so that the lithium battery industry is well developed. The main metal elements in the waste lithium ion battery comprise copper, aluminum, nickel, cobalt, manganese and lithium, and the one-by-one separation and recovery of the metal elements can generate higher production cost, have long recovery flow and long period, and are not beneficial to large-scale industrialized recovery.
The existing recovery technology of waste lithium ion batteries mainly comprises the following steps: (1) the full-wet leaching technology comprises the steps of crushing and separating the waste lithium ion battery, acid leaching, solid-liquid separation and the like, but has the problems of complex operation, high cost, difficult treatment of generated waste liquid and the like; (2) the fire method and wet method combined technology comprises the steps of crushing and stripping, oxidizing roasting, wet leaching and the like of the waste lithium ion battery, but has the problems of high energy consumption, easy generation of toxic and harmful gases and the like; (3) wet leaching and coprecipitation technology, including steps of crushing and stripping, acid leaching and separation (precipitation, complexation, extraction and other methods) of waste lithium ion batteries, can realize the recovery of high-purity nickel-cobalt-manganese ternary precursors, but the industrial crushing technology is to crush the lithium ion battery pole pieces into 10-20mm fragments, so that the complete separation of the positive pole pieces is difficult to realize; sulfuric acid and hydrogen peroxide are generally used in the acid leaching process, secondary waste liquid is generated, and meanwhile, the physical health of operators is greatly threatened.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for recovering a nickel-cobalt-manganese ternary material in a waste lithium ion battery, which can effectively solve the problems that the separation of a positive active substance from an aluminum foil is difficult and a secondary waste liquid is easy to generate in the conventional recovery method.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a method for preparing a nickel-cobalt-manganese ternary material by utilizing a waste lithium ion battery comprises the following steps:
(1) discharging the waste lithium ion battery and removing the positive plate;
(2) placing the positive plate in the step (1) in an organic solvent for ultrasonic oscillation, and separating a positive active substance;
(3) cleaning the positive active substance in the step (2) by using ultrapure water, and then carrying out suction filtration and drying;
(4) dissolving the dried positive active substance in the step (3) by using an organic acid solution, and then adding a reducing agent into the solution to form a metal ion solution;
(5) adding a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution into the metal ion solution obtained in the step (4) to obtain a salt solution;
(6) adding the salt solution and the sodium hydroxide solution obtained in the step (5) into ammonia water at the same time, adjusting the pH value of the mixed solution to be alkaline, generating a ternary precursor precipitate, and separating and drying the ternary precursor precipitate;
(7) adjusting the residual salt solution in the step (6) to be neutral, adding a saturated sodium carbonate solution into the neutral salt solution to generate lithium carbonate precipitate, and separating and drying the lithium carbonate precipitate;
(8) and (4) co-firing the ternary precursor precipitate in the step (6) and the lithium carbonate precipitate in the step (7) to obtain the lithium carbonate lithium secondary battery.
In the scheme, the disassembled positive plate and the organic solvent are subjected to ultrasonic oscillation, so that the positive active material and the aluminum foil are gradually separated, the separation and the acquisition of the positive active material are realized, the doping of aluminum elements in the aluminum foil is effectively reduced, and the problem of subsequent aluminum impurity removal is further avoided; the positive active substance is dissolved by organic acid, so that metal ions can be leached to a greater extent, and meanwhile, the generation of toxic gas can be reduced, the pollution to the environment is reduced, and the corrosion to equipment is reduced; the reducing agent is added in the leaching process, so that the dissolving-out speed of metal ions can be improved;
and then supplementing nickel sulfate, cobalt sulfate and manganese sulfate solution into the metal ion solution to ensure that the proportion of nickel, cobalt and manganese in the solution is the same as that of the prepared ternary cathode material, then adding ammonia water and sodium hydroxide into the solution to form ternary precursor precipitate, then adding sodium carbonate into the solution to generate lithium carbonate precipitate, realizing recycling of lithium ions, and finally co-firing the ternary precursor precipitate and the lithium carbonate precipitate to obtain the ternary material.
Further, the organic solvent in the step (2) is at least one of tetrahydrofuran, dimethylformamide, tetramethylurea, trimethyl phosphate and acetone.
Further, in the step (2), the organic solvent is a mixture of tetrahydrofuran and acetone, and the volume ratio of the tetrahydrofuran to the acetone is 2: 1.
In the above scheme, organic solvent is adopted as the impregnating compound, the impregnating compound can gradually permeate into the space between the positive active material and the aluminum foil, ultrasonic oscillation is matched, the positive active material and the aluminum foil can be quickly separated, then the positive active material is dissolved independently, the aluminum element in the aluminum foil can be effectively prevented from being dissolved, and the follow-up operation of impurity removal is avoided.
Further, in the step (2), ultrasonic oscillation is carried out for 1-2h under the frequency of 30-35 Hz.
In the scheme, the oscillating frequency can influence the separation, the oscillating frequency is too high, the positive electrode material is broken, the separation of the positive electrode active substance and the aluminum foil is more difficult, the oscillating frequency is too low, and the separation time is prolonged.
Further, in the step (3), the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
In the scheme, after the separated positive electrode active substance is cleaned by ultrapure water, impurity residues on the surface can be reduced, and the positive electrode active substance is dried at the temperature, so that the loss of the active substance can be avoided, and the subsequent metal ion leaching amount is increased.
Further, the organic acid solution in the step (4) is at least one of oxalic acid, formic acid, benzoic acid and acetic acid.
Further, the organic acid in the step (4) is a mixed solution of oxalic acid, formic acid and benzoic acid, and the volume ratio of the oxalic acid, the formic acid and the benzoic acid is 2:1: 1.
In the scheme, the organic acid is oxalic acid, formic acid, benzoic acid and acetic acid, the acidity of the organic acid is gradually increased, and the organic acid is adopted for dissolving, so that toxic substances can be avoided, waste liquid can not be generated, and the pollution to the environment is reduced.
Further, in the step (4), the solution is dissolved at 50-60 ℃.
In the above-described aspect, the solubility of the metal ions in the positive electrode active material increases with an increase in temperature, and the solubility of the metal ions is the greatest when the temperature is 50 to 60 ℃.
Further, the reducing agent in the step (4) is at least one of acetaldehyde, glucose, aniline and ethanol.
Further, the volume ratio of the reducing agent to the organic acid dissolving solution in the step (4) is 1: 18-22.
According to the scheme, acetaldehyde, glucose, aniline and ethanol are added as reducing agents, so that the reaction can be promoted to be carried out in the forward direction, and the dissolution rate of metal ions is effectively increased.
Further, in the step (7), the pH value is adjusted to be neutral by using an organic acid.
Further, the co-firing temperature in the step (8) is 500-.
Further, the calcination temperature in the step (8) was 800 ℃.
In the scheme, the two precipitates are fully fused by co-firing in the scheme to form the ternary material.
Further, in the step (8), the ternary precursor precipitation and the lithium carbonate precipitation are carried out according to the proportion of 1: mixing at a ratio of 1-1.2.
Further, in the step (8), the ternary precursor precipitate and the lithium carbonate precipitate are mixed according to the proportion of 1: 1.08.
The beneficial effects produced by the invention are as follows:
1. the method solves the problem that the positive active substance and the aluminum foil can not be completely separated in the recovery of the waste lithium ion battery, avoids the subsequent aluminum impurity removal problem caused by the aluminum entering the organic acid leaching solution, and improves the purity of the regenerated ternary precursor.
2. According to the method, the organic acid solution is used as the leaching solution, and reducing agents such as acetaldehyde, glucose and ethanol are added, so that metal ions can be leached to a greater extent, the generation of toxic gas in the inorganic acid leaching process is avoided, the corrosion to equipment is small, and the formed waste liquid is easier to treat.
3. The method has the advantages of low recovery cost, simple operation, easy realization of large-scale industrial production and no secondary pollution in the recovery process.
Detailed Description
Example 1
A method for preparing a nickel-cobalt-manganese ternary material by utilizing a waste lithium ion battery comprises the following steps:
(1) discharging the waste lithium ion battery (to below 2.0V), cutting the aluminum plastic film shell, and removing materials such as a positive plate, a negative plate, a diaphragm and the like;
(2) placing the positive plate in a mixed solvent of tetrahydrofuran and acetone (v: v ═ 2:1) and carrying out ultrasonic oscillation for 2h under the condition of 35Hz to thoroughly separate a positive active substance from an aluminum foil;
(3) cleaning the positive active substance with ultrapure water for 3 times, filtering, and drying at 60 deg.C for 8 hr;
(4) dissolving a positive electrode active substance in a mixed solution of oxalic acid, formic acid and benzoic acid (v: v: v is 2:1:1) at 50 ℃ for 2 hours, and then adding a glucose solution with the mass fraction of 2.5%, wherein the volume ratio of the glucose solution to the mixed acid solution is 1:18, so as to form a metal ion solution;
(5) filtering a small amount of undissolved residues in the metal ion solution, and then supplementing and adding a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution to obtain a metal ion salt solution, so that n (Ni), n (Co), and (Mn) in the final solution are 5:2: 3;
(6) adding a metal ion salt solution and a 2mol/L sodium hydroxide solution into a reaction kettle paved with 0.2mol/L ammonia water base solution by using a peristaltic pump at the speed of 2ml/min in parallel, wherein the volume ratio of the metal ion salt solution to the ammonia water to the sodium hydroxide is 1:1:2, adjusting the pH of the solution to be 11, stirring at the rotating speed of 800rpm, carrying out coprecipitation reaction to obtain a ternary precursor, washing the ternary precursor for 3 times by using ultrapure water, and drying the ternary precursor for 10 hours at the temperature of 60 ℃;
(7) adjusting the pH of the lithium-containing solution remained in the step (6) to be neutral by oxalic acid, and adding saturated sodium carbonate solution to lead Li to be neutral+Forming lithium carbonate precipitate, stopping adding when the precipitation amount is not increased, washing the lithium carbonate by ultrapure water, performing suction filtration, and drying;
(8) and mixing the ternary precursor material with lithium carbonate according to the mass ratio of 1:1, and then roasting at 500-900 ℃ in air atmosphere to obtain the 523-type ternary cathode material.
Measuring the types and the concentrations of the metal ions in the metal ion solution in the step (5) and the ternary precursor precipitate in the step (6) by ICP-OES, and concretely referring to the following table 1:
TABLE 1 content of various metal ions at different stages
Example 2
A method for preparing a nickel-cobalt-manganese ternary material by utilizing a waste lithium ion battery comprises the following steps:
(1) discharging the waste lithium ion battery (to below 2.0V), cutting the aluminum plastic film shell, and removing materials such as a positive plate, a negative plate, a diaphragm and the like;
(2) placing the positive plate in a mixed solvent of tetrahydrofuran and acetone (v: v ═ 2:1) and carrying out ultrasonic oscillation for 2h under the condition of 30Hz to thoroughly separate a positive active substance from an aluminum foil;
(3) cleaning the positive active substance with ultrapure water for 4 times, filtering, and drying at 80 ℃ for 8h for later use;
(4) dissolving the positive electrode active substance in a mixed solution of oxalic acid, formic acid and benzoic acid (v: v: v is 1:2:1) at 60 ℃ for 3 hours, adding 2.5% by mass of glucose, and enabling the volume ratio of the glucose solution to the mixed acid solution to be 1:20 to form a metal ion solution;
(5) filtering a small amount of undissolved residues in the metal ion solution, and then supplementing and adding a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution to obtain a metal ion salt solution, so that n (Ni), n (Co), and (Mn) in the final solution are 5:2: 3;
(6) adding a metal ion salt solution and a 5mol/L sodium hydroxide solution into a reaction kettle paved with 0.4mol/L ammonia water base solution by using a peristaltic pump at the speed of 2ml/min in parallel, wherein the volume ratio of the metal ion salt solution to the ammonia water to the sodium hydroxide is 1:1:2.5, adjusting the pH of the solution to 11, stirring at the rotating speed of 1200rpm, carrying out coprecipitation reaction to obtain a ternary precursor, washing the precursor for 3 times by using ultrapure water, and drying the precursor for 12 hours at the temperature of 60 ℃;
(7) adjusting the pH of the lithium-containing solution remained in the step (6) to be neutral by oxalic acid, and adding saturated sodium carbonate solution to lead Li to be+Forming lithium carbonate precipitate, stopping adding when the precipitation amount is not increased, washing the lithium carbonate by ultrapure water, performing suction filtration, and drying;
(8) and roasting the ternary precursor material and lithium carbonate at the mass ratio of 1:1.05 at 900 ℃ in an air atmosphere to obtain the 523-type ternary cathode material.
Measuring the types and the concentrations of the metal ions in the metal ion solution in the step (5) and the ternary precursor precipitate in the step (6) by ICP-OES, and concretely referring to the following table 2:
TABLE 2 content of various metal ions at different stages
Example 3
A method for preparing a nickel-cobalt-manganese ternary material by utilizing a waste lithium ion battery comprises the following steps:
(1) discharging the waste lithium ion battery (to below 2.0V), cutting the aluminum plastic film shell, and removing materials such as a positive plate, a negative plate, a diaphragm and the like;
(2) placing the positive plate in a mixed solvent of tetrahydrofuran and acetone (v: v ═ 2:1) and carrying out ultrasonic oscillation for 2h under the condition of 32Hz to thoroughly separate a positive active substance from an aluminum foil;
(3) cleaning the positive active substance with ultrapure water for 4 times, filtering, and drying at 70 deg.C for 12 h;
(4) dissolving the positive electrode active substance in a mixed solution of oxalic acid, benzoic acid and acetic acid (v: v: v: 2:1:1) at 60 ℃ for 3 hours, adding 2.5% by mass of glucose, and enabling the volume ratio of the glucose solution to the mixed acid solution to be 1:22 to form a metal ion solution;
(5) filtering a small amount of undissolved residues in the metal ion solution, and then supplementing and adding a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution to obtain a metal ion salt solution, wherein n (Ni), n (Co), and (Mn) are 5:2:3 in the final solution;
(6) adding a metal ion salt solution and a 4mol/L sodium hydroxide solution into a reaction kettle paved with 0.3mol/L ammonia water base solution by using a peristaltic pump at the speed of 2ml/min in parallel, wherein the volume ratio of the metal ion salt solution to the ammonia water to the sodium hydroxide is 1:1:2, adjusting the pH of the solution to 11, stirring at the rotating speed of 1200rpm, carrying out coprecipitation reaction to obtain a ternary precursor, washing the precursor for 3 times by using ultrapure water, and drying the precursor for 12 hours at the temperature of 60 ℃;
(7) adjusting the pH of the lithium-containing solution remained in the step (6) to be neutral by oxalic acid, and adding saturated sodium carbonate solution to lead Li to be+Forming lithium carbonate precipitate, stopping adding when the precipitation amount is not increased, washing the lithium carbonate by ultrapure water, performing suction filtration, and drying;
(8) and roasting the ternary precursor material and lithium carbonate at the mass ratio of 1:1.08 at 800 ℃ in an air atmosphere to obtain the 523-type ternary cathode material.
Measuring the types and the concentrations of the metal ions in the metal ion solution in the step (5) and the ternary precursor precipitate in the step (6) by ICP-OES, and concretely referring to the following table 3:
TABLE 3 content of various metal ions at different stages
Example 4
A method for preparing a nickel-cobalt-manganese ternary material by utilizing a waste lithium ion battery comprises the following steps:
(1) discharging the waste lithium ion battery (to below 2.0V), cutting the aluminum plastic film shell, and removing materials such as a positive plate, a negative plate, a diaphragm and the like;
(2) placing the positive plate in a mixed solvent of tetrahydrofuran and acetone (v: v ═ 2:1) and carrying out ultrasonic oscillation for 2h under the condition of 35Hz to thoroughly separate a positive active substance from an aluminum foil;
(3) cleaning the positive active substance with ultrapure water for 4 times, filtering, and drying at 80 ℃ for 10h for later use;
(4) dissolving the positive electrode active substance in a mixed solution of oxalic acid, benzoic acid and acetic acid (v: v: v ═ 1:2:1) at 55 ℃ for 3 hours, adding 2.5% by mass of glucose, and enabling the volume ratio of the glucose solution to the mixed acid solution to be 1:20 to form a metal ion solution;
(5) filtering a small amount of undissolved residues in the metal ion solution, and then supplementing and adding a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution to obtain a metal ion salt solution, so that n (Ni), n (Co), and (Mn) in the final solution are 5:2: 3;
(6) adding a metal ion salt solution and a 3mol/L sodium hydroxide solution into a reaction kettle paved with 0.4mol/L ammonia water base solution by using a peristaltic pump at the speed of 2ml/min in parallel, adjusting the pH of the solution to 11, stirring at the rotating speed of 1200rpm, carrying out coprecipitation reaction to obtain a ternary precursor, washing the precursor for 3 times by using ultrapure water, and drying at the temperature of 60 ℃ for 12 hours;
(7) adjusting the pH of the lithium-containing solution remained in the step (6) to be neutral by oxalic acid, and adding saturated sodium carbonate solution to lead Li to be+Forming lithium carbonate precipitate, stopping adding when the precipitation amount is not increased, washing the lithium carbonate by ultrapure water, performing suction filtration, and drying;
(8) and roasting the ternary precursor material and lithium carbonate at the mass ratio of 1:1.01 in an air atmosphere at 800 ℃ to obtain the 523-type ternary cathode material.
Measuring the types and the concentrations of the metal ions in the metal ion solution in the step (5) and the ternary precursor precipitate in the step (6) by ICP-OES, and concretely referring to the following table 4:
TABLE 4 content of various metal ions at different stages
Example 5
A method for preparing a nickel-cobalt-manganese ternary material by utilizing a waste lithium ion battery comprises the following steps:
(1) discharging the waste lithium ion battery (to below 2.0V), cutting the aluminum plastic film shell, and removing materials such as a positive plate, a negative plate, a diaphragm and the like;
(2) placing the positive plate in a mixed solvent of dimethylformamide and tetramethylurea (v: v ═ 2:1) and carrying out ultrasonic oscillation for 1-2h under the condition of 33Hz to thoroughly separate a positive active substance from an aluminum foil;
(3) cleaning the positive active substance with ultrapure water for 4 times, filtering, and drying at 75 ℃ for 12h for later use;
(4) dissolving the positive electrode active substance in a solution of formic acid, benzoic acid and acetic acid (v: v: v ═ 2:2:1) at 60 ℃ for 3 hours, adding an ethanol solution with the mass fraction of 2.5%, wherein the volume ratio of the ethanol solution to the mixed acid solution is 1:20, and forming a metal ion solution;
(5) filtering undissolved residues in the metal ion solution, and then supplementing and adding a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution to obtain a metal ion salt solution, so that n (Ni), n (Co), and (Mn) in the final solution are 5:2: 3;
(6) adding a metal ion salt solution and a 5mol/L sodium hydroxide solution into a reaction kettle paved with 0.4mol/L ammonia water base solution by using a peristaltic pump at the speed of 2ml/min in parallel, wherein the volume ratio of the metal ion salt solution to the ammonia water to the sodium hydroxide is 1:1:2, adjusting the pH of the solution to 11, stirring at the rotating speed of 1000rpm, carrying out coprecipitation reaction to obtain a ternary precursor, washing the precursor for 3 times by using ultrapure water, and drying at the temperature of 60 ℃ for 12 hours;
(7) adjusting the pH of the lithium-containing solution remained in the step (6) to be neutral by oxalic acid, and adding saturated sodium carbonate solution to lead Li to be+Forming lithium carbonate precipitate, stopping adding when the precipitation amount is not increased, washing the lithium carbonate by ultrapure water, performing suction filtration, and drying;
(8) and roasting the ternary precursor material and lithium carbonate at the mass ratio of 1:1.05 at 900 ℃ in an air atmosphere to obtain the 523-type ternary cathode material.
Measuring the types and concentrations of the metal ions in the metal ion solution in the step (5) and the ternary precursor precipitate in the step (6) by ICP-OES, and concretely referring to Table 5:
TABLE 5 content of various metal ions at different stages
Example 6
A method for preparing a nickel-cobalt-manganese ternary material by utilizing a waste lithium ion battery comprises the following steps:
(1) discharging the waste lithium ion battery (to below 2.0V), cutting the aluminum plastic film shell, and removing materials such as a positive plate, a negative plate, a diaphragm and the like;
(2) placing the positive plate in a mixed solvent of tetrahydrofuran and acetone (v: v ═ 2:1) and carrying out ultrasonic oscillation for 2h under the condition of 35Hz to thoroughly separate a positive active substance from an aluminum foil;
(3) cleaning the positive active substance with ultrapure water for 4 times, filtering, and drying at 80 deg.C for 8-12 h;
(4) dissolving the positive electrode active substance in a mixed solution of formic acid, benzoic acid and acetic acid (v: v: v ═ 3:1:1) at 60 ℃ for 3 hours, adding an ethanol solution with the mass fraction of 2.5%, wherein the volume ratio of the ethanol solution to the mixed acid solution is 1:20, and forming a metal ion solution;
(5) filtering undissolved residues in the metal ion solution, and then supplementing and adding a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution to obtain a metal ion salt solution, so that n (Ni), n (Co), and (Mn) in the final solution are 5:2: 3;
(6) adding a metal ion salt solution and a 5mol/L sodium hydroxide solution into a reaction kettle paved with 0.4mol/L ammonia water base solution by using a peristaltic pump at the speed of 2ml/min in parallel, wherein the volume ratio of the metal ion salt solution to the ammonia water to the sodium hydroxide is 1:1:2, adjusting the pH of the solution to be 11, stirring at the rotating speed of 1200rpm, carrying out coprecipitation reaction to obtain a ternary precursor, washing the precursor for 3 times by using ultrapure water, and drying the precursor for 10-12h at the temperature of 60 ℃;
(7) adjusting the pH of the lithium-containing solution remained in the step (6) to be neutral by oxalic acid, and adding saturated sodium carbonate solution to lead Li to be+Forming lithium carbonate precipitate, stopping adding when the precipitation amount is not increased, washing the lithium carbonate by ultrapure water, performing suction filtration, and drying;
(8) and roasting the ternary precursor material and lithium carbonate at the mass ratio of 1:1.07 at 700 ℃ in an air atmosphere to obtain the 523-type ternary cathode material.
Measuring the types and the concentrations of the metal ions in the metal ion solution in the step (5) and the ternary precursor precipitate in the step (6) by ICP-OES, and concretely referring to the following table 6:
TABLE 6 content of various metal ions at different stages
The data in tables 1-6 show that the nickel, cobalt and manganese elements in the anode material can be effectively extracted according to the method in the application, the content of iron impurities in the extract is low, and the content of iron impurities in the ternary precursor precipitate generated after the precipitation reaction is extremely low, so that the requirement of raw materials for preparing the nickel, cobalt and manganese ternary battery is met.
Claims (10)
1. A method for preparing a nickel-cobalt-manganese ternary material by utilizing a waste lithium ion battery is characterized by comprising the following steps of:
(1) discharging the waste lithium ion battery, and detaching a positive plate;
(2) placing the positive plate in the step (1) in an organic solvent for ultrasonic oscillation, and separating a positive active substance;
(3) cleaning the positive active substance in the step (2) by using ultrapure water, and then carrying out suction filtration and drying;
(4) dissolving the dried positive active substance in the step (3) by using an organic acid solution, and then adding a reducing agent into the solution to form a metal ion solution;
(5) adding a nickel sulfate solution, a cobalt sulfate solution and a manganese sulfate solution into the metal ion solution obtained in the step (4) to obtain a salt solution;
(6) adding a sodium hydroxide solution and ammonia water into the salt solution obtained in the step (5) at the same time, adjusting the pH value of the mixed solution to be alkaline, generating a ternary precursor precipitate, and separating and drying the ternary precursor precipitate;
(7) adjusting the residual salt solution in the step (6) to be neutral, adding a sodium carbonate solution into the neutral salt solution to generate a lithium carbonate precipitate, and separating and drying the lithium carbonate precipitate;
(8) and (4) co-firing the ternary precursor precipitate in the step (6) and the lithium carbonate precipitate in the step (7) to obtain the lithium carbonate lithium secondary battery.
2. The method for preparing the nickel-cobalt-manganese ternary material by using the waste lithium ion batteries according to claim 1, wherein the organic solvent in the step (2) is at least one of tetrahydrofuran, dimethylformamide, tetramethylurea, trimethyl phosphate and acetone.
3. The method for preparing the nickel-cobalt-manganese ternary material by using the waste lithium ion batteries according to claim 1 or 2, wherein the organic solvent in the step (2) is a mixture of tetrahydrofuran and acetone, and the volume ratio of the tetrahydrofuran to the acetone is 2-2.5: 1.
4. The method for preparing the nickel-cobalt-manganese ternary material by using the waste lithium ion batteries as claimed in claim 1, wherein in the step (2), the ultrasonic oscillation is carried out for 1-2h at the frequency of 30-35 Hz.
5. The method for preparing the nickel-cobalt-manganese ternary material by using the waste lithium ion batteries as claimed in claim 1, wherein the drying temperature in the step (3) is 60-80 ℃, and the drying time is 8-12 h.
6. The method for preparing the nickel-cobalt-manganese ternary material by using the waste lithium ion batteries as claimed in claim 1, wherein the organic acid solution in the step (4) is at least one of oxalic acid, formic acid, benzoic acid and acetic acid.
7. The method for preparing the nickel-cobalt-manganese ternary material by utilizing the waste lithium ion batteries as claimed in claim 1 or 6, wherein the organic acid in the step (4) is a mixed solution of oxalic acid, formic acid and benzoic acid, and the volume ratio of the oxalic acid, the formic acid and the benzoic acid is 1-2:1-2: 1-2.
8. The method for preparing the nickel-cobalt-manganese ternary material by using the waste lithium ion batteries as claimed in claim 1, wherein the positive active material in the step (4) is dissolved in organic acid at 50-60 ℃.
9. The method for preparing the nickel-cobalt-manganese ternary material by using the waste lithium ion batteries according to claim 1, wherein the reducing agent in the step (4) is at least one of acetaldehyde, glucose, aniline and ethanol.
10. The method for preparing the nickel-cobalt-manganese ternary material by using the waste lithium ion batteries as claimed in claim 1, wherein the volume ratio of the reducing agent to the organic acid solution in the step (4) is 1: 18-22.
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Application publication date: 20201120 |