CN114875243B - Eutectic solvent, preparation method thereof and leaching method of lithium battery anode material - Google Patents
Eutectic solvent, preparation method thereof and leaching method of lithium battery anode material Download PDFInfo
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- CN114875243B CN114875243B CN202210458210.XA CN202210458210A CN114875243B CN 114875243 B CN114875243 B CN 114875243B CN 202210458210 A CN202210458210 A CN 202210458210A CN 114875243 B CN114875243 B CN 114875243B
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- hydrogen bond
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- eutectic solvent
- battery anode
- waste lithium
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- 238000002386 leaching Methods 0.000 title claims abstract description 86
- 239000002904 solvent Substances 0.000 title claims abstract description 71
- 230000005496 eutectics Effects 0.000 title claims abstract description 70
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 40
- 239000010405 anode material Substances 0.000 title claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 80
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 80
- 239000002699 waste material Substances 0.000 claims abstract description 65
- 238000010438 heat treatment Methods 0.000 claims abstract description 47
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 150000002739 metals Chemical class 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229960003403 betaine hydrochloride Drugs 0.000 claims abstract description 13
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical group [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 37
- 229910001416 lithium ion Inorganic materials 0.000 claims description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 239000006183 anode active material Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 5
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 5
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 claims description 4
- 229910012748 LiNi0.5Mn0.3Co0.2O2 Inorganic materials 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 7
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 abstract description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 abstract description 4
- 229960003237 betaine Drugs 0.000 abstract description 4
- 150000007524 organic acids Chemical class 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- 230000001698 pyrogenic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 235000005985 organic acids Nutrition 0.000 abstract 1
- 239000000370 acceptor Substances 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 235000019743 Choline chloride Nutrition 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 229960003178 choline chloride Drugs 0.000 description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical group [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 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
- 230000009471 action Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction 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
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007787 solid Substances 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1658—Leaching with acyclic or carbocyclic agents of different types in admixture, e.g. with organic acids added to oximes
-
- 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
-
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a eutectic solvent, a preparation method thereof and a leaching method of a waste lithium battery anode material, wherein the eutectic solvent is a mixture composed of a hydrogen bond acceptor and a hydrogen bond donor, and is prepared by mixing the hydrogen bond acceptor and the hydrogen bond donor and then heating and stirring, and the hydrogen bond acceptor comprises at least one of betaine, thiobetaine and betaine hydrochloride; hydrogen bond donors include reducing alcohols or organic acids; and leaching valuable metals in the waste lithium battery anode material by using the eutectic solvent. The eutectic solvent has low raw material price, wide sources, easy acquisition, low preparation cost, cyclic utilization and recovery cost reduction; the leaching method of valuable metals in the waste lithium battery anode material can replace the traditional pyrogenic process and the wet process with strong acid and strong alkali as a leaching agent, achieves the purpose of green and environment protection, has leaching rate of more than 90 percent and high recovery efficiency.
Description
Technical Field
The invention relates to the technical field of waste lithium ion battery material recovery, in particular to a eutectic solvent, a preparation method thereof and a leaching method of waste lithium battery anode material.
Background
Lithium ion batteries are widely and largely used as excellent carriers of electric energy, however, the service life of lithium ion batteries is 3 to 6 years. Therefore, from the waste materials, scraps and pole pieces produced in each process of the full life cycle of the lithium ion battery to the dead battery materials in the retired battery, a great amount of positive electrode materials need to be recycled. At present, the research on waste lithium ion batteries is widely focused, and the recycling of valuable metals mainly has two stages of work, namely, pretreatment of the waste batteries is carried out, and the aim is to obtain purer positive electrode active materials and prepare for subsequent recycling; secondly, the anode material is recycled, namely valuable metals such as cobalt, lithium, nickel, manganese and the like are extracted.
At present, the main modes of industrially recycling valuable metals (nickel, cobalt, manganese and lithium) in waste lithium batteries are a fire method and a wet method or a combined mode of the fire method and the wet method. In the pyrogenic process, unavoidable disadvantages such as high operating temperature, high implementation cost, and harmful exhaust gas emissions exist; in the wet process, the cost problem, the purity of recovered metal and the recovery rate can be effectively solved, but the use of common leaches such as strong acid and alkali can cause the problems of secondary waste liquid and environmental pollution, and meanwhile, acid-base leaches can damage equipment and increase the recovery cost.
Disclosure of Invention
The invention provides a eutectic solvent, a preparation method thereof and a leaching method of a waste lithium battery anode material, which are used for solving the technical problems of low leaching rate and non-environment-friendly leaching process of the existing leaching method of the waste lithium battery anode material.
In order to solve the technical problems, the invention adopts the following technical scheme:
a eutectic solvent, the eutectic solvent being a mixture of hydrogen bond acceptors and hydrogen bond donors, the hydrogen bond acceptors including at least one of betaine, thiobetaine and betaine hydrochloride; the hydrogen bond donor is included in a reducing alcohol or an organic acid.
The thinking of the technical proposal is that different hydrogen bond acceptors, different hydrogen bond donors and different eutectic solvent properties are formed, and the dissolving capacity of the eutectic solvent to metal oxide is also different. Generally, hydrogen bond donors, if reducing, will promote leaching of the metal oxide; the stronger the acidity of the hydrogen bond donor is, the better the leaching effect is; the stronger the complexing action of the hydrogen bond donor on the metal ions, the stronger the capability of forming a complex with the hydrogen bond donor; the invention obtains the eutectic solvent with excellent leaching effect on the anode material of the waste lithium ion battery through selecting the types and the collocations of the hydrogen bond donor and the acceptor, and the hydrogen bond donor and the acceptor have low raw material price, wide sources and easy obtainment, thereby reducing the production and subsequent use cost.
As a further preferable aspect of the above technical solution, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor in the eutectic solvent is (1:9) to (1:1). In the eutectic solvent system, the ratio of the hydrogen bond acceptor to the hydrogen bond donor is also a key parameter influencing the leaching effect, and after multiple experiments and repeated researches, the specific hydrogen bond acceptor and the hydrogen bond donor in the molar ratio range are mutually matched, so that the optimal leaching effect on the waste lithium ion battery anode material can be obtained. The more and more stable the low melting solvent formed, the more soluble the metal oxide at the preferred molar ratio.
As a further preferable aspect of the above technical solution, when the hydrogen bond donor selects an organic acid, the eutectic solvent further includes water, and the addition amount of the water is less than 42% of the mass of the eutectic solvent.
As a further preferable aspect of the above technical scheme, the reducing alcohol includes at least one of ethanol, ethylene glycol and polyethylene glycol; the organic acid comprises at least one of citric acid, formic acid, p-toluenesulfonic acid, oxalic acid, malonic acid and glutaric acid. Citric acid, formic acid, p-toluenesulfonic acid, oxalic acid, malonic acid and glutaric acid can provide more hydrogen ions, so that dissolution of materials is promoted; and ethanol, glycol and polyethylene glycol have reducibility, and can reduce metal ions, so that the metal ions in low valence state are easier to leach out. Meanwhile, the formed eutectic solvent can generate complexation action on metal ions to promote the dissolution of metals.
Based on the same technical conception, the invention also provides a preparation method of the eutectic solvent, which comprises the following operations: mixing the hydrogen bond acceptor and the hydrogen bond donor, and then heating and stirring to obtain the eutectic solvent; the heating temperature is 80-120 ℃, and the heating and stirring time is 0.1-2 h.
Based on the same technical conception, the invention also provides a leaching method of valuable metals in the waste lithium battery anode material, which utilizes the eutectic solvent for leaching; the leaching method comprises the following operations: and adding the waste lithium battery anode material into the eutectic solvent, heating and stirring for a set time, and filtering to obtain the leaching solution containing valuable metals.
As a further preferable mode of the technical scheme, the liquid-solid ratio of the eutectic solvent to the waste lithium battery anode material is 10-50 g/g.
As a further preferable mode of the above-mentioned technical scheme, the heating temperature at the time of leaching is 80 to 200 ℃. The temperature of the system during leaching has great influence on the effect of leaching the anode material by the eutectic solvent, and the leaching effect of the anode material of the waste lithium ion battery is optimal under the temperature condition after repeated experiments and repeated researches.
As a further preference of the above technical scheme, the leaching time is 0.5-24h.
As a further preferable mode of the technical scheme, the waste lithium battery anode material is pretreated and then added into the eutectic solvent for leaching, and the pretreatment comprises pyrolysis, water leaching and filtering which are sequentially carried out.
As a further preferable aspect of the above technical solution, the pyrolysis operation temperature is 600 ℃ and the pyrolysis operation time is 2h.
As a further preference of the technical scheme, the waste lithium battery positive electrode material comprises one or two of lithium cobalt oxide positive electrode material, lithium manganate positive electrode material and lithium nickel cobalt manganate positive electrode material.
Compared with the prior art, the invention has the advantages that:
(1) The eutectic solvent has low raw material price, wide sources, easy acquisition, low preparation cost, cyclic utilization and recovery cost reduction;
(2) The leaching method of valuable metals in the waste lithium battery anode material can replace the traditional pyrogenic process and the wet process with strong acid and strong alkali as a leaching agent, achieves the purpose of environmental protection, has leaching rate of more than 90%, and has good leaching effect, short leaching time and high recovery efficiency.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
The eutectic solvent of this embodiment is a mixture of a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is a thiobetaine, the hydrogen bond donor is ethylene glycol, and the molar ratio of the thiobetaine to the ethylene glycol is 1:5.
The preparation method of the eutectic solvent of the present embodiment includes the following operations: mixing the thiobetaine and the glycol according to the proportion, and heating and stirring to obtain a eutectic solvent; the heating temperature is 120 ℃, and the heating and stirring time is 1.5h.
The leaching method of valuable metals in the waste ternary lithium battery anode material LiNi 0.5Mn0.3Co0.2O2 comprises the following steps:
(1) Pyrolyzing the waste lithium ion battery anode material at 600 ℃ for 2 hours, leaching with water, filtering and separating aluminum foil to obtain a waste lithium ion battery anode active material;
(2) Mixing 20g of the eutectic solvent of the embodiment with 0.5g of waste lithium ion battery anode active material powder, and heating and leaching for 5 hours at 140 ℃ to obtain a mixed solution;
(3) Filtering the mixed solution to obtain a leaching solution, and measuring the contents of nickel, cobalt, manganese and lithium in the leaching solution by ICP to obtain leaching rates of Ni=90.47%, gu=90.89%, mn=90.91% and Li= 92.98%, respectively.
Example 2:
the eutectic solvent in this embodiment is a mixture of a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is betaine hydrochloride, the hydrogen bond donor is ethylene glycol, and the molar ratio of betaine hydrochloride to ethylene glycol is 1:6.
The preparation method of the eutectic solvent of the present embodiment includes the following operations: mixing the hydrogen bond acceptor and the hydrogen bond donor in the proportion, and heating and stirring to obtain a eutectic solvent; the heating temperature is 100 ℃, and the heating and stirring time is 2 hours.
The leaching method of valuable metals in the waste lithium battery anode material (LiNi 0.5Co0.2Mn0.3O2) comprises the following steps:
(1) Pyrolyzing the waste lithium cobalt oxide battery anode material at 600 ℃ for 2 hours, leaching with water, filtering and separating aluminum foil to obtain a waste lithium ion battery anode active material;
(2) Mixing 30g of the eutectic solvent of the embodiment with 0.5g of waste lithium ion battery anode active material powder, and heating and leaching for 8 hours at 200 ℃ to obtain a mixed solution;
(3) And filtering the mixed solution to obtain a leaching solution, and measuring the cobalt and lithium contents in the leaching solution by ICP to obtain leaching rates of Li=97.98% and Co=90.89%, respectively.
Example 3:
The eutectic solvent of this embodiment is a mixture of a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is betaine hydrochloride, the hydrogen bond donor is polyethylene glycol, and the molar ratio of the thiobetaine to the polyethylene glycol is 1:1.
The preparation method of the eutectic solvent of the present embodiment includes the following operations: mixing betaine hydrochloride and polyethylene glycol according to the proportion, and heating and stirring to obtain a eutectic solvent; the heating temperature is 120 ℃, and the heating and stirring time is 1.5h.
The leaching method of valuable metals in the waste ternary lithium battery anode material LiNi 0.5Mn0.3Co0.2O2 comprises the following steps:
(1) Pyrolyzing the waste lithium ion battery anode material at 600 ℃ for 2 hours, leaching with water, filtering and separating aluminum foil to obtain a waste lithium ion battery anode active material;
(2) Mixing 20g of the eutectic solvent of the embodiment with 0.5g of waste lithium ion battery anode active material powder, and heating and leaching for 5 hours at 140 ℃ to obtain a mixed solution;
(3) The mixed solution is filtered to obtain leaching solution, and the content of nickel, cobalt, manganese and lithium in the leaching solution is measured by ICP, so that leaching rates of Ni=78.31%, gu= 80.31%, mn=79.11% and Li=90.55% are obtained.
Example 4:
the eutectic solvent in this embodiment is a mixture of a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is betaine, the hydrogen bond donor is ethanol, and the molar ratio of betaine to ethanol is 1:9.
The preparation method of the eutectic solvent of the present embodiment includes the following operations: mixing the hydrogen bond acceptor and the hydrogen bond donor in the proportion, and heating and stirring to obtain a eutectic solvent; the heating temperature is 100 ℃, and the heating and stirring time is 1.5h.
The leaching method of valuable metals in the waste lithium battery anode material comprises the following steps:
(1) Pyrolyzing a waste lithium cobalt oxide battery anode material (LiCoO 2) at 600 ℃ for 2 hours, leaching with water, filtering and separating aluminum foil to obtain a waste lithium ion battery anode active material;
(2) Mixing 30g of the eutectic solvent of the embodiment with 0.5g of waste lithium ion battery anode active material powder, and heating and leaching for 20 hours at 100 ℃ to obtain a mixed solution;
(3) And filtering the mixed solution to obtain a leaching solution, and measuring the cobalt and lithium contents in the leaching solution by ICP to obtain leaching rates of Li=65.65% and Co=68.44%, respectively.
Example 5:
The eutectic solvent of this embodiment is a mixture of a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is a thiobetaine, the hydrogen bond donor is citric acid, and the molar ratio of the thiobetaine to the citric acid is 1:3.
The preparation method of the eutectic solvent of the present embodiment includes the following operations: mixing the thiobetaine and the citric acid in the proportion, and heating and stirring (the water addition amount is 30% of the total mass) after mixing to obtain a eutectic solvent; the heating temperature is 70 ℃, and the heating and stirring time is 30min.
The leaching method of valuable metals in the waste ternary lithium battery anode material (LiNi 0.5Co0.2Mn0.3O2) comprises the following steps:
(1) Removing the binder and the aluminum foil from the waste lithium ion battery anode material to obtain a waste lithium ion battery anode active material;
(2) 26g of the eutectic solvent of the embodiment is mixed with 0.5g of waste lithium ion battery anode active material powder, and the mixture is heated and leached for 30min at 100 ℃ to obtain a mixed solution;
(3) Filtering the mixed solution to obtain a leaching solution, and measuring the contents of nickel, cobalt, manganese and lithium in the leaching solution by ICP to obtain leaching rates of E Ni＝87.76％、EGu＝88.45％、EMn＝89.39％、ELi = 88.90%, respectively.
Example 6:
the eutectic solvent in this embodiment is a mixture of a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is betaine hydrochloride, the hydrogen bond donor is p-toluenesulfonic acid, and the molar ratio of betaine hydrochloride to p-toluenesulfonic acid is 1:1.
The preparation method of the eutectic solvent of the present embodiment includes the following operations: mixing the hydrogen bond acceptor and the hydrogen bond donor in the proportion, and heating and stirring to obtain a eutectic solvent; the heating temperature is 70 ℃, and the heating and stirring time is 30min.
The leaching method of valuable metals in the ternary positive electrode material of the waste lithium battery comprises the following steps:
(1) Removing binder and aluminum foil from the waste lithium cobalt oxide battery anode material to obtain a waste lithium ion battery anode active material;
(2) 36g of the eutectic solvent of the embodiment is mixed with 0.5g of waste lithium ion battery anode active material powder, and the mixture is heated and leached for 15min at 100 ℃ to obtain a mixed solution;
(3) Filtering the mixed solution to obtain leaching solution, and measuring the cobalt and lithium content in the leaching solution by ICP to obtain leaching rates of E Ni＝90.78％、EGu＝89.47％、EMn＝89.34％、ELi =98.21%, respectively.
Example 7:
The eutectic solvent in this embodiment is a mixture of a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is betaine hydrochloride, the hydrogen bond donor is oxalic acid, and the molar ratio of betaine hydrochloride to polyethylene glycol is 1:1.
The preparation method of the eutectic solvent of the present embodiment includes the following operations: mixing betaine hydrochloride, polyethylene glycol and water in the proportion, and heating and stirring (the water addition amount is 30% of the total mass) to obtain a eutectic solvent; the heating temperature is 70 ℃, and the heating and stirring time is 1h.
The leaching method of valuable metal (LiNi 0.5Co0.2Mn0.3O2) in the waste ternary lithium battery anode material of the embodiment comprises the following steps:
(1) Removing the binder and the aluminum foil from the waste lithium ion battery anode material to obtain a waste lithium ion battery anode active material;
(2) 26g of the eutectic solvent of the embodiment is mixed with 0.5g of waste lithium ion battery anode active material powder, and the mixture is heated and leached for 60min at 100 ℃ to obtain a mixed solution;
(3) Filtering the mixed solution to obtain a leaching solution, and measuring the contents of nickel, cobalt, manganese and lithium in the leaching solution by ICP to obtain leaching rates of E Ni＝0.1％、ECo＝0.5％、EMn＝0.4％、ELi =98.90%, respectively.
Comparative example 1:
The eutectic solvent of the comparative example is a mixture of a hydrogen bond acceptor and a hydrogen bond donor, and as a comparative experiment, the hydrogen bond acceptor is choline chloride, the hydrogen bond donor is ethylene glycol, and the molar ratio of choline chloride to ethylene glycol is 1:5.
The preparation method of the eutectic solvent of the comparative example comprises the following operations: mixing the thiobetaine and the glycol according to the proportion, and heating and stirring to obtain a eutectic solvent; the heating temperature is 120 ℃, and the heating and stirring time is 1.5h.
The leaching method of valuable metals in the waste ternary lithium battery anode material LiNi 0.5Mn0.3Co0.2O2 of the comparative example comprises the following steps:
(1) Pyrolyzing the waste lithium ion battery anode material at 600 ℃ for 2 hours, leaching with water, filtering and separating aluminum foil to obtain a waste lithium ion battery anode active material;
(2) Mixing 20g of the eutectic solvent of the embodiment with 0.5g of waste lithium ion battery anode active material powder, and heating and leaching at 140 ℃ for 60min to obtain a mixed solution;
(3) The mixed solution is filtered to obtain leaching solution, and the content of nickel, cobalt, manganese and lithium in the leaching solution is measured by ICP, so that leaching rates of Ni=10.3%, co=12.89%, mn=11.91% and Li=22.98% are obtained.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. A leaching method of valuable metals in a waste lithium battery anode material is characterized in that,
The leaching method of valuable metals in the waste ternary lithium battery anode material LiNi 0.5Mn0.3Co0.2O2 comprises the following steps:
(1) Pyrolyzing the waste lithium ion battery anode material at 600 ℃ for 2 hours, leaching with water, filtering and separating aluminum foil to obtain a waste lithium ion battery anode active material;
(2) Mixing 20g of eutectic solvent with 0.5g of waste lithium ion battery anode active material powder, and heating and leaching for 5 hours at 140 ℃ to obtain a mixed solution; wherein the eutectic solvent is a mixture composed of a hydrogen bond acceptor and a hydrogen bond donor, the hydrogen bond acceptor is thiobetaine, the hydrogen bond donor is ethylene glycol, and the molar ratio of the thiobetaine to the ethylene glycol is 1:5, the preparation method of the eutectic solvent comprises the following operations: mixing the thiobetaine and the glycol according to the proportion, and then heating and stirring to obtain the eutectic solvent, wherein the heating temperature is 120 ℃, and the heating and stirring time is 1.5h;
(3) Filtering the mixed solution to obtain a leaching solution;
Or the leaching method of valuable metals in the waste ternary lithium battery anode material LiNi 0.5Co0.2Mn0.3O2 comprises the following steps:
(1) Removing the binder and the aluminum foil from the waste lithium ion battery anode material to obtain a waste lithium ion battery anode active material;
(2) Mixing 26g of eutectic solvent with 0.5g of waste lithium ion battery anode active material powder, and heating and leaching for 30min at 100 ℃ to obtain a mixed solution; wherein the eutectic solvent is a mixture composed of a hydrogen bond acceptor and a hydrogen bond donor, the hydrogen bond acceptor is thiobetaine, the hydrogen bond donor is citric acid, and the molar ratio of the thiobetaine to the citric acid is 1:3, the preparation method of the eutectic solvent comprises the following operations: mixing the thiobetaine and the citric acid in the proportion, and heating and stirring after mixing with water to obtain the eutectic solvent, wherein the heating temperature is 70 ℃, and the heating and stirring time is 30min;
(3) Filtering the mixed solution to obtain a leaching solution;
or the leaching method of valuable metals in the ternary positive electrode material of the waste lithium battery comprises the following steps:
(1) Removing binder and aluminum foil from the waste lithium cobalt oxide battery anode material to obtain a waste lithium ion battery anode active material;
(2) Mixing 36g of eutectic solvent with 0.5g of waste lithium ion battery anode active material powder, and heating and leaching for 15min at 100 ℃ to obtain a mixed solution; the eutectic solvent is a mixture composed of a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is betaine hydrochloride, the hydrogen bond donor is p-toluenesulfonic acid, the molar ratio of the betaine hydrochloride to the p-toluenesulfonic acid is 1:1, and the preparation method of the eutectic solvent comprises the following operations: mixing the hydrogen bond acceptor and the hydrogen bond donor in the proportion, and heating and stirring to obtain the eutectic solvent, wherein the heating temperature is 70 ℃, and the heating and stirring time is 30min;
(3) Filtering the mixed solution to obtain a leaching solution.
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