CN114875243A - Eutectic solvent, preparation method thereof and leaching method of lithium battery positive electrode material - Google Patents

Eutectic solvent, preparation method thereof and leaching method of lithium battery positive electrode material Download PDF

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CN114875243A
CN114875243A CN202210458210.XA CN202210458210A CN114875243A CN 114875243 A CN114875243 A CN 114875243A CN 202210458210 A CN202210458210 A CN 202210458210A CN 114875243 A CN114875243 A CN 114875243A
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leaching
hydrogen bond
eutectic solvent
positive electrode
electrode material
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张晨阳
罗毅
欧乐明
孙伟
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Central South University
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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
    • 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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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Secondary Cells (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a eutectic solvent and a preparation method thereof and a leaching method of a waste lithium battery anode material, wherein the eutectic solvent is a mixture consisting of a hydrogen bond acceptor and a hydrogen bond donor, and is prepared by mixing, heating and stirring the hydrogen bond acceptor and the hydrogen bond donor, wherein the hydrogen bond acceptor comprises at least one of betaine, thio-betaine and betaine hydrochloride; hydrogen bond donors include reducing alcohols or organic acids; valuable metals in the anode material of the waste lithium battery are leached by the eutectic solvent. The eutectic solvent has the advantages of low price of raw materials, wide sources, easy obtainment, low preparation cost, cyclic utilization and reduced recovery cost; the leaching method of the valuable metals in the waste lithium battery positive electrode material can replace the traditional pyrogenic process and the wet process using strong acid and strong base as leaching agents, so that the purpose of environmental protection is achieved, the leaching rate can reach more than 90%, and the recovery efficiency is high.

Description

Eutectic solvent, preparation method thereof and leaching method of lithium battery positive electrode material
Technical Field
The invention relates to the technical field of waste lithium ion battery material recovery, in particular to a eutectic solvent and a preparation method thereof, and a leaching method of a waste lithium battery anode material.
Background
Lithium ion batteries are widely and abundantly used as excellent carriers of electric energy, but the service life of lithium ion batteries is 3 to 6 years. Therefore, a great amount of positive electrode materials are needed to be recycled and reused from waste materials, leftover materials and electrode sheet materials produced in all processes of the whole life cycle of the lithium ion battery to the failed battery materials in the retired battery. At present, research on waste lithium ion batteries is widely concerned, and valuable metal recycling mainly comprises two stages of work, namely waste battery pretreatment, which aims to obtain a purer positive active material and prepare for subsequent recycling; and secondly, recycling the anode material, namely extracting the valuable metals such as cobalt, lithium, nickel, manganese and the like.
At present, the main mode for industrially recycling valuable metals (nickel, cobalt, manganese and lithium) in waste lithium batteries is a pyrogenic process and a wet process or a combined mode of the pyrogenic process and the wet process. In the pyrometallurgical process, there are inevitable disadvantages such as high operating temperature, high cost of implementation, and harmful exhaust emission; in the wet process, the cost problem, the recovered metal purity and the recovery rate can be effectively solved, but the problems of secondary waste liquid and environmental pollution can be caused by using common leaching agents such as strong acid, strong base and the like, and meanwhile, the acid-base leaching agent 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 that the leaching rate is low and the leaching process is not environment-friendly in 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, wherein the eutectic solvent is a mixture consisting of a hydrogen bond acceptor and a hydrogen bond donor, and the hydrogen bond acceptor comprises at least one of betaine, thiobetaine and betaine hydrochloride; the hydrogen bond donor is included in a reducing alcohol or organic acid.
The idea of the technical scheme is that different hydrogen bond acceptors and different hydrogen bond donors form eutectic solvents with different properties and different dissolving capacities for metal oxides. Generally, hydrogen bond donors, if reductive, will promote leaching of the metal oxide; the stronger the acidity of the hydrogen bond donor, the better the leaching effect; the stronger the hydrogen bond donor has to complex with metal ions, the stronger the ability to form complexes with the metal ions; according to the invention, the eutectic solvent with excellent leaching effect on the anode material of the waste lithium ion battery is obtained by selecting the types of the hydrogen bond donor and the acceptor and matching the hydrogen bond donor and the acceptor, and the hydrogen bond donor and the acceptor are low in raw material price, wide in source and easy to obtain, so that the production and subsequent use costs can be reduced.
In a further preferred embodiment of the present invention, 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 proportion of the hydrogen bond acceptor and the hydrogen bond donor is also a key parameter influencing the leaching effect, and after a plurality of tests 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 anode material of the waste lithium ion battery can be obtained. Under the condition of the optimal molar ratio, the more and more stable the formed low-melting solvent is, the stronger the dissolving capacity for the metal oxide is.
As a further preferred mode of the above technical solution, when the hydrogen bond donor is selected from organic acids, the eutectic solvent further comprises water, and the amount of water added is less than 42% of the mass of the eutectic solvent.
As a further preferred aspect of the above technical solution, the reducing alcohol comprises at least one of ethanol, ethylene glycol and polyethylene glycol; the organic acid includes 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 the dissolution of materials is promoted; and the ethanol, the glycol and the polyethylene glycol have reducibility, and can reduce metal ions, so that the metal ions in a low valence state are easier to leach out. Meanwhile, the formed eutectic solvent can generate complexation to metal ions to promote the dissolution of metal.
Based on the same technical concept, 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 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 concept, the invention also provides a leaching method of valuable metals in the anode material of the waste lithium battery, which utilizes the eutectic solvent for leaching; the leaching method comprises the following operations: and adding the waste lithium battery positive electrode material into the eutectic solvent, heating and stirring for a set time, and filtering to obtain a leaching solution containing valuable metals.
As a further optimization of the technical scheme, the liquid-solid ratio of the eutectic solvent to the anode material of the waste lithium battery is 10-50 g/g.
As a further optimization of the technical scheme, the heating temperature during leaching is 80-200 ℃. The temperature of the system during leaching has great influence on the effect of leaching the cathode material by the eutectic solvent, and after a plurality of tests and repeated researches, the leaching effect of the cathode material of the waste lithium ion battery is optimal under the temperature condition.
As a further optimization of the technical proposal, the leaching time is 0.5 to 24 hours.
As a further preferred aspect of the above technical solution, the waste lithium battery positive electrode material is pretreated and then added to the eutectic solvent for leaching, and the pretreatment includes pyrolysis, water leaching and filtration operations performed in sequence.
As a further optimization of the technical scheme, the pyrolysis operation temperature is 600 ℃, and the pyrolysis operation time is 2 h.
Preferably, the waste lithium battery pack positive electrode material comprises one or two of a lithium cobaltate positive electrode material, a lithium manganate positive electrode material and a lithium nickel cobalt manganese oxide positive electrode material.
Compared with the prior art, the invention has the advantages that:
(1) the eutectic solvent has the advantages of low price of raw materials, wide sources, easy obtainment, low preparation cost, cyclic utilization and reduced recovery cost;
(2) the leaching method of the valuable metals in the waste lithium battery positive electrode material can replace the traditional pyrogenic process and the wet process using strong acid and strong base as leaching agents, achieves the aim of environmental protection, has leaching rate of over 90 percent, 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 in this embodiment is a mixture of a hydrogen bond acceptor and a hydrogen bond donor, wherein 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 of the embodiment includes the following operations: mixing the thiobetaine and the ethylene glycol according to the proportion, and then heating and stirring to obtain a eutectic solvent; the heating temperature is 120 ℃, and the heating and stirring time is 1.5 h.
LiNi which is a positive electrode material of waste ternary lithium battery 0.5 Mn 0.3 Co 0.2 O 2 The leaching method of the medium valuable metal comprises the following steps:
(1) pyrolyzing the anode material of the waste lithium ion battery for 2 hours at 600 ℃, and then obtaining the anode active material of the waste lithium ion battery after water immersion, filtration and separation of aluminum foil;
(2) mixing 20g of the eutectic solvent and 0.5g of powder of the anode active material of the waste lithium ion battery, and leaching by heating at 140 ℃ for 5 hours to obtain a mixed solution;
(3) the mixed solution was filtered to obtain a leachate, and the contents of nickel, cobalt, manganese, and lithium in the leachate were measured by ICP to obtain leaching rates of 90.47% Ni, 90.89% Gu, 90.91% Mn, and 92.98% Li, 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 the betaine hydrochloride to the ethylene glycol is 1: 6.
The preparation method of the eutectic solvent of the present example includes the following operations: mixing the hydrogen bond acceptor and the hydrogen bond donor in the proportion, and then heating and stirring to obtain a eutectic solvent; the heating temperature is 100 ℃, and the heating and stirring time is 2 h.
The positive electrode material (LiNi) of the waste lithium battery of the embodiment 0.5 Co 0.2 Mn 0.3 O 2 ) The leaching method of the medium valuable metal comprises the following steps:
(1) pyrolyzing the anode material of the waste lithium cobaltate ion battery at 600 ℃ for 2h, and then carrying out water immersion, filtration and separation on aluminum foil to obtain the anode active material of the waste lithium ion battery;
(2) mixing 30g of the eutectic solvent and 0.5g of powder of the anode active material of the waste lithium ion battery, and heating and leaching at 200 ℃ for 8 hours to obtain a mixed solution;
(3) the mixed solution was filtered to obtain a leachate, and the cobalt and lithium contents in the leachate were measured by ICP to obtain leaching rates of 97.98% for Li and 90.89% for Co, respectively.
Example 3:
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 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 example includes the following operations: mixing the betaine hydrochloride and the 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 1.5 h.
LiNi which is a positive electrode material of waste ternary lithium battery 0.5 Mn 0.3 Co 0.2 O 2 The leaching method of the medium valuable metal comprises the following steps:
(1) pyrolyzing the anode material of the waste lithium ion battery for 2 hours at 600 ℃, and then obtaining the anode active material of the waste lithium ion battery after water immersion, filtration and separation of aluminum foil;
(2) mixing 20g of the eutectic solvent and 0.5g of waste lithium ion battery anode active material powder, and heating and leaching at 140 ℃ for 5 hours to obtain a mixed solution;
(3) the mixed solution was filtered to obtain a leachate, and the contents of nickel, cobalt, manganese, and lithium in the leachate were measured by ICP to obtain leaching rates of 78.31% Ni, 80.31% Gu, 79.11% Mn, and 90.55% Li, respectively.
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 the betaine to the ethanol is 1: 9.
The preparation method of the eutectic solvent of the present example includes the following operations: mixing the hydrogen bond acceptor and the hydrogen bond donor in the proportion, and then heating and stirring to obtain a eutectic solvent; the heating temperature is 100 ℃, and the heating and stirring time is 1.5 h.
The leaching method of valuable metals in the positive electrode material of the waste lithium battery in the embodiment comprises the following steps:
(1) positive electrode material (LiCoO) of waste lithium cobaltate ion battery 2 ) Pyrolyzing the mixture for 2 hours at 600 ℃, and then obtaining the anode active material of the waste lithium ion battery after water immersion, filtration and separation of aluminum foil;
(2) mixing 30g of the eutectic solvent and 0.5g of powder of the anode active material of the waste lithium ion battery, and heating and leaching at 100 ℃ for 20 hours to obtain a mixed solution;
(3) the mixed solution was filtered to obtain a leachate, and the cobalt and lithium contents in the leachate were measured by ICP to obtain leaching rates of Li 65.65% and Co 68.44%, respectively.
Example 5:
the eutectic solvent in this embodiment is a mixture of a hydrogen bond acceptor and a hydrogen bond donor, where 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 of the present example includes the following operations: mixing the above-mentioned ratio of thiobetaine and citric acid with water, heating and stirring (the water addition quantity is 30% of total mass) so as to obtain eutectic solvent; the heating temperature is 70 deg.C, and the heating stirring time is 30 min.
The waste ternary lithium battery cathode material (LiNi) of the embodiment 0.5 Co 0.2 Mn 0.3 O 2 ) The leaching method of the medium valuable metal 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 the eutectic solvent and 0.5g of waste lithium ion battery anode active material powder, and heating and leaching at 100 ℃ for 30min to obtain a mixed solution;
(3) filtering the mixed solution to obtain a leaching solution, measuring the contents of nickel, cobalt, manganese and lithium in the leaching solution by ICP (inductively coupled plasma), and obtaining leaching rates E Ni ＝87.76％、E Gu ＝88.45％、E Mn ＝89.39％、E Li ＝88.90％。
Example 6:
the eutectic solvent in this example 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 example 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 deg.C, and the heating stirring time is 30 min.
The leaching method of valuable metals in the ternary cathode material of the waste lithium battery comprises the following steps:
(1) removing the binder and the aluminum foil from the waste lithium cobaltate ion battery positive electrode material to obtain a waste lithium ion battery positive electrode active material;
(2) mixing 36g of the eutectic solvent and 0.5g of powder of the anode active material of the waste lithium ion battery, and heating and leaching at 100 ℃ for 15min to obtain a mixed solution;
(3) filtering the mixed solution to obtain a leaching solution, measuring the contents of cobalt and lithium in the leaching solution by ICP (inductively coupled plasma), and obtaining leaching rates E N i＝90.78％、E Gu ＝89.47％、E Mn ＝89.34％、E Li ＝98.21％。
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 the betaine hydrochloride to the polyethylene glycol is 1: 1.
the preparation method of the eutectic solvent of the present example includes the following operations: mixing the betaine hydrochloride, the polyethylene glycol and the water according to the proportion, and then heating and stirring (the water addition amount is 30 percent of the total mass) to obtain a eutectic solvent; the heating temperature is 70 ℃, and the heating and stirring time is 1 h.
Valuable metal (LiNi) in the anode material of the waste ternary lithium battery of the embodiment 0.5 Co 0.2 Mn 0.3 O 2 ) The leaching method 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 the eutectic solvent and 0.5g of powder of the anode active material of the waste lithium ion battery, and heating and leaching at 100 ℃ for 60min to obtain a mixed solution;
(3) filtering the mixed solution to obtain a leaching solution, measuring the contents of nickel, cobalt, manganese and lithium in the leaching solution by ICP (inductively coupled plasma), and obtaining leaching rates E Ni ＝0.1％、E Co ＝0.5％、E Mn ＝0.4％、E Li ＝98.90％。
Comparative example 1:
the eutectic solvent of this comparative example is the mixture that hydrogen bond acceptor and hydrogen bond donor are constituteed, and as the contrast experiment, the hydrogen bond acceptor is choline chloride, and the hydrogen bond donor is ethylene glycol, and the mol ratio of choline chloride and ethylene glycol is 1: 5.
the preparation method of the eutectic solvent of the present comparative example includes the following operations: mixing the thiobetaine and the ethylene glycol according to the proportion, and then heating and stirring to obtain a eutectic solvent; the heating temperature is 120 ℃, and the heating and stirring time is 1.5 h.
LiNi which is the anode material of the waste ternary lithium battery of the comparative example 0.5 Mn 0.3 Co 0.2 O 2 The leaching method of the medium valuable metal comprises the following steps:
(1) pyrolyzing the anode material of the waste lithium ion battery for 2 hours at 600 ℃, and then obtaining the anode active material of the waste lithium ion battery after water immersion, filtration and separation of aluminum foil;
(2) mixing 20g of the eutectic solvent and 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 was filtered to obtain a leachate, and the contents of nickel, cobalt, manganese and lithium in the leachate were measured by ICP to obtain leaching rates of 10.3% Ni, 12.89% Co, 11.91% Mn and 22.98% Li, respectively.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The eutectic solvent is characterized in that the eutectic solvent is a mixture consisting of a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor comprises at least one of betaine, thiobetaine and betaine hydrochloride; the hydrogen bond donor includes a reducing alcohol or an organic acid.
2. The eutectic solvent according to claim 1, wherein the molar ratio of the hydrogen bond acceptor and the hydrogen bond donor in the eutectic solvent is (1: 9) to (1: 1).
3. The eutectic solvent according to claim 1, wherein the reducing alcohol comprises at least one of ethanol, ethylene glycol and polyethylene glycol; the organic acid includes at least one of citric acid, formic acid, p-toluenesulfonic acid, oxalic acid, malonic acid, and glutaric acid.
4. A method for preparing the eutectic solvent according to any one of claims 1 to 3, comprising the operations of: mixing the hydrogen bond acceptor and the hydrogen bond donor, and heating and stirring to obtain the eutectic solvent; the heating temperature is 25-120 ℃, and the heating and stirring time is 0.1-2 h.
5. A leaching method of valuable metals in positive electrode materials of waste lithium batteries, which is characterized in that the eutectic solvent of any one of claims 1 to 3 is used for leaching; the leaching method comprises the following operations: and adding the waste lithium battery positive electrode material into the eutectic solvent, heating and stirring for a set time, and filtering to obtain a leaching solution containing valuable metals.
6. The method for leaching valuable metals from the positive electrode material of the waste lithium battery as claimed in claim 5, wherein the liquid-solid ratio of the eutectic solvent to the positive electrode material of the waste lithium battery is 10-50 g/g.
7. The method for leaching valuable metals from the positive electrode material of waste lithium batteries as claimed in claim 5, wherein the heating temperature during leaching is 60-200 ℃.
8. The method for leaching valuable metals from the positive electrode material of waste lithium batteries as recited in claim 5, wherein the leaching time is 0.5-24 hours.
9. The method for leaching valuable metals from the positive electrode material of the waste lithium battery as claimed in claim 5, wherein the positive electrode material of the waste lithium battery is pretreated and then added into the eutectic solvent for leaching, and the pretreatment comprises pyrolysis, water leaching and filtering operations which are sequentially carried out.
10. The method for leaching valuable metals from the waste lithium battery positive electrode material as claimed in claim 5, wherein the waste lithium battery positive electrode material comprises one or two of a lithium cobaltate positive electrode material, a lithium manganate positive electrode material and a nickel cobalt lithium manganate positive electrode material.
CN202210458210.XA 2022-04-27 2022-04-27 Eutectic solvent, preparation method thereof and leaching method of lithium battery positive electrode material Pending CN114875243A (en)

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