CN111807417A - Method for dissolving and extracting lithium cobaltate by using polyglycol/thiourea type eutectic solvent - Google Patents
Method for dissolving and extracting lithium cobaltate by using polyglycol/thiourea type eutectic solvent Download PDFInfo
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- CN111807417A CN111807417A CN202010349146.2A CN202010349146A CN111807417A CN 111807417 A CN111807417 A CN 111807417A CN 202010349146 A CN202010349146 A CN 202010349146A CN 111807417 A CN111807417 A CN 111807417A
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Abstract
The application discloses a method for dissolving and extracting lithium cobaltate by using a polyglycol/thiourea eutectic solvent, which comprises the following steps: 1) stirring and mixing polyethylene glycol 200 and thiourea in an oil bath pan according to a molar ratio to form a polyglycol/thiourea eutectic solvent; 2) crushing the lithium battery positive electrode recycled material to prepare mixed powder containing lithium cobaltate; 3) weighing part of the eutectic solvent prepared in the step 1), adding the mixed powder containing lithium cobaltate prepared in the step 2), and continuously heating and stirring for a period of time until the mixed powder containing lithium cobaltate is dissolved in the eutectic solvent and reaches a saturated state, so as to prepare a lithium cobaltate extraction solvent; 4) centrifuging the lithium cobaltate extraction solvent prepared in the step 3). The invention has the advantages that the invention can overcome the defects of the prior art, and has simple method, easy operation, mild condition, cheap raw materials and environmental protection.
Description
Technical Field
The invention relates to a method for dissolving and extracting lithium cobaltate by using a polyglycol/thiourea eutectic solvent, belonging to the field of lithium ion battery waste recovery.
Background
The lithium ion battery is the most widely used secondary battery at present, and has the advantages of low self-discharge rate, smooth discharge and the like. The lithium ion battery can supply power for a cardiac pacemaker implanted into a human body, is also suitable for supplying power for an integrated circuit, is widely applied to equipment such as notebook computers, intelligent wearable equipment, digital cameras, mobile phones and the like, and also has important functions in power stations and uninterrupted power supplies of some post and telecommunications equipment and in industry, military and aviation. With the increasing demand for lithium ions, the waste of batteries is increasing. Lithium cobaltate is commonly used as a positive electrode material of a lithium battery, and is a positive electrode material with excellent electrochemical properties. The lithium cobaltate is easy to process and has low average attenuation, and the lithium cobaltate is used as the anode material of the battery, so that the volume specific capacity of the battery can be improved, and the performance of the lithium battery can be more stable.
Therefore, the development of a method for dissolving and extracting lithium cobaltate is one of the keys of the recovery of the waste lithium ion battery.
The main method for dissolving lithium cobaltate commonly used at present is acid leaching, which comprises using strong acid (such as hydrochloric acid, sulfuric acid, nitric acid), strong base (such as sodium hydroxide) or organic acid (such as citric acid, oxalic acid), and the detailed patent numbers are as follows: CN201910938060.0, CN201210179652.7, CN201310095245.2 and CN 201910946969.0. The disadvantages of this method are: easily corrode equipment, generate a large amount of waste liquid and damage the ecological environment. The mixed aqueous solution of peroxodisulfate and formate also has a certain solubility for lithium cobaltate, as described in the prior patent No. CN 201910602754.7. However, this method produces a large amount of waste water solution, and the peroxodisulfate has very strong oxidizing property, is easily decomposed, and is highly irritant.
The eutectic solvent is a Novel substance discovered by Abbott in 2003 [ Abbott, A.P., Capper, G., Davies, D.L., Rasheed, R.K. & Tambyrajah, V., Novel solvent properties of chlorine/urea mixturej.Chem.Commun.2003, 70-71], a Novel green solvent and a designable solvent [ Paiva, A.A., Craveiro, R, Aroso, I.A., Martins, M.Reis, R.L. & Duarte, A.R.C., Natural deep eutectoics-solvents for the 21. sub.21. Sustan.3, 2014.2014.3, 2014.2014 ] which have the advantages of simple synthesis, low cost, high biodegradability, high designability, and are considered to be 21. The waste lithium ion battery is recovered by using the eutectic solvent, and the method is environment-friendly, strong in operability and good in application prospect.
Tran et al used choline chloride/ethylene glycol as a eutectic solvent to dissolve lithium cobaltate for the first time, but had better dissolution effect at a high temperature of 150 [ Tran, M.K., Rodrigues, M.T.F., Kato, K., Babu, G. & Ajayan, P.M., Deep electronic solutions for cathode recycling of Li-ion batteries [ J ] Nature Energy 2019,4, 339-. Rold n-Ruiz found that p-Toluenesulfonic Acid/water/choline chloride DESS have higher solubility [ Rold n-Ruiz, M.J., Ferrer, M.L., Gutierrez, M.C. & Del Monte, F., HighlyEffective p-Toluenesulfonic Acid-Based Deep-European solutions for Cathododerecycling of Li-ion Batteries [ J ]. Sustainable Chem.Eng.2020, DOI: 10.1021/ussecheme.1020c00 ], but its raw material Toluenesulfonic Acid has strong acidity (892-1.3), close to that of sulfuric Acid (pKa-3), and puts high demands on industrial mass production equipment. In view of the above technical deficiencies, it is desirable to provide a eutectic solvent extraction method which is convenient for production and can better dissolve and extract lithium cobaltate at low temperature.
Disclosure of Invention
The invention provides a method for dissolving and extracting lithium cobaltate by using a polyglycol/thiourea type eutectic solvent, which has the advantages of low material energy consumption, environmental friendliness, mild conditions and simple operation, and is an economic and safe extraction method.
In order to solve the technical problems, the invention adopts the technical scheme that the method for dissolving and extracting the lithium cobaltate by utilizing the polyglycol/thiourea eutectic solvent comprises the following steps:
1) stirring and mixing polyethylene glycol 200 and thiourea in an oil bath pan according to a molar ratio to form a polyglycol/thiourea eutectic solvent;
2) crushing the lithium battery positive electrode recycled material to prepare mixed powder containing lithium cobaltate;
3) weighing part of the eutectic solvent prepared in the step 1), adding the mixed powder containing lithium cobaltate prepared in the step 2), and continuously heating and stirring for a period of time until the mixed powder containing lithium cobaltate is dissolved in the eutectic solvent and reaches a saturated state, so as to prepare a lithium cobaltate extraction solvent;
4) carrying out centrifugal operation on the lithium cobaltate extraction solvent prepared in the step 3);
5) carrying out ICP-OES detection on part of supernatant of the centrifuged lithium cobaltate extraction solvent, and determining the dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent;
6) after the dissolution concentration of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent is determined to reach the dissolution standard in the step 5), continuously taking the supernatant of the lithium cobaltate extraction solvent after the step 4), and continuously carrying out secondary centrifugation operation;
7) taking the supernatant of the lithium cobaltate extraction solvent after the step 6);
8) adding distilled water into the residual solvent residue after the supernatant liquid is taken out in the step 7), stirring, standing and taking the supernatant liquid after standing;
9) and mixing the supernatant liquid taken out in the step 8) with the supernatant liquid taken out in the step 7), and drying to prepare the lithium cobaltate.
Preferably, in the method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea eutectic solvent, in the step 1), the molar ratio of the polyethylene glycol 200 to the thiourea is 5:1 to 1:1, and the specific molar ratio of the polyethylene glycol 200 to the thiourea is 2: 1.
Preferably, in the method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea eutectic solvent, in the step 1), the temperature of the eutectic solvent is 20-90 ℃ and the time is 4-12 hours.
Preferably, in the method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea eutectic solvent, in the step 1), the temperature of the eutectic solvent is 30 ℃ and the time is 8 hours.
Preferably, in the method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea type eutectic solvent, in the step 3), the mass ratio of the eutectic solvent to the mixed powder containing lithium cobaltate is 100:1 to 10:1, and specifically, the mass ratio of the eutectic solvent to the mixed powder containing lithium cobaltate is 50: 1.
Preferably, in the method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea eutectic solvent, in the step 3), the temperature of the eutectic solvent in the process of dissolving the mixed powder containing the lithium cobaltate is 30-100 ℃, and the dissolving time is 0.1-48 hours.
Preferably, in the method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea eutectic solvent, in the step 3), the temperature of the eutectic solvent in the process of dissolving the mixed powder containing the lithium cobaltate is 80 ℃, and the dissolving time is 12 hours.
Preferably, in the method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea eutectic solvent, in the steps 4) and 6), the centrifugal rate is 10000 rpm, and the centrifugal time is 10 minutes.
Preferably, in the method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea type eutectic solvent, in the step 5), the process of measuring the dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent needs to be repeated three times, and the average value of the three measured concentrations is taken as the final dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent.
Preferably, in the method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea type eutectic solvent, after the dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent are measured to reach the standard in the step 5), the operation of the step 6) is carried out; the standard of the dissolution concentration of lithium cobaltate in the lithium cobaltate extraction solvent is as follows: the PPM concentration of cobalt ions in the lithium cobaltate extraction solvent is greater than or equal to 1200 and the PPM concentration of lithium cobaltate in the lithium cobaltate extraction solvent is greater than or equal to 2000.
According to the technical scheme, the eutectic solvent formed by mixing the polyethylene glycol 200 and the thiourea is used as a solvent for dissolving the lithium cobaltate in the lithium battery positive electrode recovery material, the eutectic solvent formed by mixing the polyethylene glycol 200 and the thiourea is cheap and safe in component, and the polyethylene glycol 200 and the thiourea can be associated through hydrogen bond interaction to form a eutectic mixture and can provide or receive electrons or protons to form hydrogen bonds, so that the lithium cobaltate has good dissolving performance. The synthesis of a eutectic solvent formed by mixing polyethylene glycol 200 and thiourea is 100 atom economical, low cost, easy to handle and does not require purification, thus making it amenable to large scale preparation. Compared with a high-temperature calcination method and an acid leaching method, the eutectic solvent formed by mixing the polyethylene glycol 200 and the thiourea is low in energy consumption for dissolving lithium, environment-friendly, mild in condition and simple to operate, and is an economic and safe extraction method.
In the application, the process of measuring the dissolved concentrations of the lithium cobaltate and the cobalt ions in the lithium cobaltate extraction solvent needs to be repeated three times, and the average value of the three measurements is taken, so that the measurement stability is improved, and the influence of interference factors on concentration measurement is reduced. In the process of dissolving the mixed powder containing the lithium cobaltate, multiple centrifugal operations are adopted to increase the centrifugal separation degree, so that the impurities in the supernatant of the lithium cobaltate extraction solvent are reduced, and the extraction purity of the lithium cobaltate is improved.
Drawings
FIG. 1 is a graph showing the content change of lithium cobaltate dissolved in a polyglycol/thiourea eutectic solvent at 80 ℃ for different times;
FIG. 2 is a graph showing the change in the content of lithium cobaltate dissolved in a polyglycol/thiourea-type eutectic solvent at different temperatures for 12 hours;
FIG. 3 is a graph showing the change in the content of lithium cobaltate dissolved in a polyglycol/thiourea-type eutectic solvent at different temperatures for 24 hours;
FIG. 4 is a table showing the content of lithium cobaltate dissolved in a polyglycol/thiourea-type eutectic solvent at 80 ℃ for different heating times;
FIG. 5 is a table showing the content of lithium cobaltate dissolved in a polyglycol/thiourea-type eutectic solvent at various temperatures for 12 hours;
FIG. 6 is a content table of lithium cobaltate dissolved by the polyglycol/thiourea type eutectic solvent at various temperatures for 24 hours.
Detailed Description
The technical features of the present invention will be further explained with reference to the accompanying drawings and specific embodiments.
Example 1
A method for dissolving and extracting lithium cobaltate by using a polyglycol/thiourea eutectic solvent comprises the following steps:
1) stirring and mixing polyethylene glycol 200 and thiourea in an oil bath pan according to a molar ratio to form a polyglycol/thiourea eutectic solvent; the molar ratio of the polyethylene glycol 200 to the thiourea is 5: 1; the formation temperature of the eutectic solvent is 20 ℃, and the time is 4 hours;
2) crushing the lithium battery positive electrode recycled material to prepare mixed powder containing lithium cobaltate;
3) weighing part of the eutectic solvent prepared in the step 1), adding the mixed powder containing lithium cobaltate prepared in the step 2), and continuously heating and stirring for a period of time until the mixed powder containing lithium cobaltate is dissolved in the eutectic solvent and reaches a saturated state, so as to prepare a lithium cobaltate extraction solvent; the mass ratio of the eutectic solvent to the mixed powder containing lithium cobaltate is 100: 1; the temperature of the eutectic solvent in the process of dissolving the mixed powder containing lithium cobaltate is 30 ℃, and the dissolving time is 0.1 hour;
4) carrying out centrifugal operation on the lithium cobaltate extraction solvent prepared in the step 3); the centrifugation speed is 10000 r/min, and the centrifugation time is 10 min;
5) carrying out ICP-OES detection on part of supernatant of the centrifuged lithium cobaltate extraction solvent, and determining the dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent; the process of measuring the dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent needs to be repeated three times, the average value of the three measured concentrations is taken, and the average value is taken as the final dissolved concentrations of the lithium cobaltate and the cobalt ions in the lithium cobaltate extraction solvent; after the dissolution concentration of the lithium cobaltate and the cobalt ions in the lithium cobaltate extraction solvent is measured to reach the standard, the operation of the step 6) is carried out; the standard of the dissolution concentration of lithium cobaltate in the lithium cobaltate extraction solvent is as follows: PPM concentration of cobalt ions in the lithium cobaltate extraction solvent is more than or equal to 1300, and PPM concentration of lithium cobaltate in the lithium cobaltate extraction solvent is more than or equal to 2100;
6) after the dissolution concentration of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent is determined to reach the dissolution standard in the step 5), continuously taking the supernatant of the lithium cobaltate extraction solvent after the step 4), and continuously carrying out secondary centrifugation operation; the centrifugation rate of the secondary centrifugation operation is 10000 r/min, and the centrifugation time is 10 min;
7) taking the supernatant of the lithium cobaltate extraction solvent after the step 6);
8) adding distilled water into the residual solvent residue after the supernatant liquid is taken out in the step 7), stirring, standing and taking the supernatant liquid after standing;
9) and mixing the supernatant liquid taken out in the step 8) with the supernatant liquid taken out in the step 7), and drying to prepare the lithium cobaltate.
Example 2
This embodiment differs from the above embodiment in that: a method for dissolving and extracting lithium cobaltate by using a polyglycol/thiourea eutectic solvent comprises the following steps:
1) stirring and mixing polyethylene glycol 200 and thiourea in an oil bath pan according to a molar ratio to form a polyglycol/thiourea eutectic solvent; the molar ratio of the polyethylene glycol 200 to the thiourea is 1: 1; the formation temperature of the eutectic solvent is 90 ℃, and the time is 12 hours;
2) crushing the lithium battery positive electrode recycled material to prepare mixed powder containing lithium cobaltate;
3) weighing part of the eutectic solvent prepared in the step 1), adding the mixed powder containing lithium cobaltate prepared in the step 2), and continuously heating and stirring for a period of time until the mixed powder containing lithium cobaltate is dissolved in the eutectic solvent and reaches a saturated state, so as to prepare a lithium cobaltate extraction solvent; the mass ratio of the eutectic solvent to the mixed powder containing lithium cobaltate is 10: 1; the temperature of the eutectic solvent in the process of dissolving the mixed powder containing lithium cobaltate is 100 ℃, and the dissolving time is 48 hours;
4) carrying out centrifugal operation on the lithium cobaltate extraction solvent prepared in the step 3); the centrifugation speed is 10000 r/min, and the centrifugation time is 10 min;
5) carrying out ICP-OES detection on part of supernatant of the centrifuged lithium cobaltate extraction solvent, and determining the dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent; the process of measuring the dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent needs to be repeated three times, the average value of the three measured concentrations is taken, and the average value is taken as the final dissolved concentrations of the lithium cobaltate and the cobalt ions in the lithium cobaltate extraction solvent; after the dissolution concentration of the lithium cobaltate and the cobalt ions in the lithium cobaltate extraction solvent is measured to reach the standard, the operation of the step 6) is carried out; the standard of the dissolution concentration of lithium cobaltate in the lithium cobaltate extraction solvent is as follows: the PPM concentration of cobalt ions in the lithium cobaltate extraction solvent is more than 1400 and the PPM concentration of lithium cobaltate in the lithium cobaltate extraction solvent is more than 2200;
6) after the dissolution concentration of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent is determined to reach the dissolution standard in the step 5), continuously taking the supernatant of the lithium cobaltate extraction solvent after the step 4), and continuously carrying out secondary centrifugation operation; the centrifugation rate of the secondary centrifugation operation is 10000 r/min, and the centrifugation time is 10 min;
7) taking the supernatant of the lithium cobaltate extraction solvent after the step 6);
8) adding distilled water into the residual solvent residue after the supernatant liquid is taken out in the step 7), stirring, standing and taking the supernatant liquid after standing;
9) and mixing the supernatant liquid taken out in the step 8) with the supernatant liquid taken out in the step 7), and drying to prepare the lithium cobaltate.
Example 3
This embodiment differs from the above embodiment in that: a method for dissolving and extracting lithium cobaltate by using a polyglycol/thiourea eutectic solvent comprises the following steps:
1) stirring and mixing polyethylene glycol 200 and thiourea in an oil bath pan according to a molar ratio to form a polyglycol/thiourea eutectic solvent; the molar ratio of the polyethylene glycol 200 to the thiourea is 2: 1; the temperature of the eutectic solvent is 30 ℃ and the time is 8 hours;
2) crushing the lithium battery positive electrode recycled material to prepare mixed powder containing lithium cobaltate;
3) weighing part of the eutectic solvent prepared in the step 1), adding the mixed powder containing lithium cobaltate prepared in the step 2), and continuously heating and stirring for a period of time until the mixed powder containing lithium cobaltate is dissolved in the eutectic solvent and reaches a saturated state, so as to prepare a lithium cobaltate extraction solvent; the mass ratio of the eutectic solvent to the mixed powder containing lithium cobaltate is 50: 1; the temperature of the eutectic solvent in the process of dissolving the mixed powder containing lithium cobaltate is 80 ℃, and the dissolving time is 12 hours;
4) carrying out centrifugal operation on the lithium cobaltate extraction solvent prepared in the step 3); the centrifugation speed is 10000 r/min, and the centrifugation time is 10 min;
5) carrying out ICP-OES detection on part of supernatant of the centrifuged lithium cobaltate extraction solvent, and determining the dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent; the process of measuring the dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent needs to be repeated three times, the average value of the three measured concentrations is taken, and the average value is taken as the final dissolved concentrations of the lithium cobaltate and the cobalt ions in the lithium cobaltate extraction solvent; after the dissolution concentration of the lithium cobaltate and the cobalt ions in the lithium cobaltate extraction solvent is measured to reach the standard, the operation of the step 6) is carried out; the standard of the dissolution concentration of lithium cobaltate in the lithium cobaltate extraction solvent is as follows: PPM concentration of cobalt ions in the lithium cobaltate extraction solvent is more than or equal to 1200, and PPM concentration of lithium cobaltate in the lithium cobaltate extraction solvent is more than or equal to 2000;
6) after the dissolution concentration of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent is determined to reach the dissolution standard in the step 5), continuously taking the supernatant of the lithium cobaltate extraction solvent after the step 4), and continuously carrying out secondary centrifugation operation; the centrifugation rate of the secondary centrifugation operation is 10000 r/min, and the centrifugation time is 10 min;
7) taking the supernatant of the lithium cobaltate extraction solvent after the step 6);
8) adding distilled water into the residual solvent residue after the supernatant liquid is taken out in the step 7), stirring, standing and taking the supernatant liquid after standing;
9) and mixing the supernatant liquid taken out in the step 8) with the supernatant liquid taken out in the step 7), and drying to prepare the lithium cobaltate.
Example 4
A method for dissolving and extracting lithium cobaltate by using a polyglycol/thiourea eutectic solvent comprises the following steps: 0.2 mole of polyethylene glycol 200 and 0.1 mole of thiourea were weighed and stirred at 80 ℃ for 3 hours to form a eutectic solvent. 5 g of the prepared eutectic solvent was weighed, 0.1 g of lithium cobaltate was added, and the mixture was stirred in an oil bath pan at 80 ℃ for 0.17 hour, 0.5 hour, 1 hour, 2 hours, 4 hours, 6 hours, 12 hours, and 24 hours, respectively. After the reaction was completed, the mixture was centrifuged at 10000 rpm for 10 minutes. Taking the supernatant to carry out ICP-OES detection. The rotation speed of each oil bath pan needs to be kept consistent so as to avoid generating errors, and the temperature of the oil bath pan needs to be corrected so as to ensure the consistency.
Example 5
This embodiment differs from the above embodiment in that: a method for dissolving and extracting lithium cobaltate by using a polyglycol/thiourea eutectic solvent comprises the following steps: 0.2 mole of polyethylene glycol 200 and 0.1 mole of thiourea were weighed and stirred at 80 ℃ for 3 hours to form a eutectic solvent. 5 g of prepared eutectic solvent is weighed, 0.1 g of lithium cobaltate is added, and the mixture is stirred in an oil bath kettle for 12 hours at the reaction temperatures of 25 ℃, 40 ℃, 60 ℃ and 80 ℃. After the reaction was completed, the mixture was centrifuged at 10000 rpm for 10 minutes. Taking the supernatant to carry out ICP-OES detection.
Example 6
This embodiment differs from the above embodiment in that: a method for dissolving and extracting lithium cobaltate by using a polyglycol/thiourea eutectic solvent comprises the following steps: 0.2 mole of polyethylene glycol 200 and 0.1 mole of thiourea were weighed and stirred at 60 ℃ for 3 hours to form a eutectic solvent. 5 g of prepared eutectic solvent is weighed, 0.1 g of lithium cobaltate is added, and the mixture is stirred in an oil bath kettle for 24 hours at the reaction temperatures of 25 ℃, 40 ℃, 60 ℃ and 80 ℃. After the reaction was completed, the mixture was centrifuged at 10000 rpm for 10 minutes. Taking the supernatant to carry out ICP-OES detection.
Example 7
This embodiment differs from the above embodiment in that: a method for dissolving and extracting lithium cobaltate by using a polyglycol/thiourea eutectic solvent comprises the following steps: 0.4 mole of polyethylene glycol 200 and 0.1 mole of thiourea were weighed and stirred at 80 ℃ for 3 hours to form a eutectic solvent. 5 g of the prepared eutectic solvent was weighed, 0.1 g of lithium cobaltate was added, and the mixture was stirred in an oil bath pan at 80 ℃ for 0.17 hour, 0.5 hour, 1 hour, 2 hours, 4 hours, 6 hours, 12 hours, and 24 hours, respectively. After the reaction was completed, the mixture was centrifuged at 10000 rpm for 10 minutes. Taking the supernatant to carry out ICP-OES detection.
In order to verify the influence of each parameter on the extraction, in examples 4 to 7, the variation of different parameters is verified, and the rotation speed of each oil bath pan is kept consistent in the verification process so as not to generate errors, for example, if a plurality of oil bath pans are used, the temperature of the oil bath pans needs to be corrected so as to ensure the consistency.
Drawing a cobalt standard curve: cobalt standards curves at 1ppm, 3ppm, 5ppm, 7ppm and 10ppm were prepared with 1 mol/l nitric acid using the national Standard sample GSB 04-1722-2004. The data were plotted as a standard curve, as measured by ICP-OES (inductively coupled plasma Optical Emission spectrometer).
The dissolved eutectic solvent containing lithium cobaltate was centrifuged at 10000 rpm for 10 minutes, and the supernatant was taken and dissolved in 1 mol/l nitric acid for ICP-OES detection. The amount of dissolved lithium cobaltate in different cases was calculated from the cobalt standard curve.
The data of fig. 4 to 6 and 1 to 3 are obtained by the verification of examples 4 to 7.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art should understand that they can make various changes, modifications, additions and substitutions within the spirit and scope of the present invention.
Claims (10)
1. A method for dissolving and extracting lithium cobaltate by using a polyglycol/thiourea eutectic solvent is characterized in that: the method comprises the following steps:
1) stirring and mixing polyethylene glycol 200 and thiourea in an oil bath pan according to a molar ratio to form a polyglycol/thiourea eutectic solvent;
2) crushing the lithium battery positive electrode recycled material to prepare mixed powder containing lithium cobaltate;
3) weighing part of the eutectic solvent prepared in the step 1), adding the mixed powder containing lithium cobaltate prepared in the step 2), and continuously heating and stirring for a period of time until the mixed powder containing lithium cobaltate is dissolved in the eutectic solvent and reaches a saturated state, so as to prepare a lithium cobaltate extraction solvent;
4) carrying out centrifugal operation on the lithium cobaltate extraction solvent prepared in the step 3);
5) carrying out ICP-OES detection on part of supernatant of the centrifuged lithium cobaltate extraction solvent, and determining the dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent;
6) after the dissolution concentration of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent is determined to reach the dissolution standard in the step 5), continuously taking the supernatant of the lithium cobaltate extraction solvent after the step 4), and continuously carrying out secondary centrifugation operation;
7) taking the supernatant of the lithium cobaltate extraction solvent after the step 6);
8) adding distilled water into the residual solvent residue after the supernatant liquid is taken out in the step 7), stirring, standing and taking the supernatant liquid after standing;
9) and mixing the supernatant liquid taken out in the step 8) with the supernatant liquid taken out in the step 7), and drying to prepare the lithium cobaltate.
2. The method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea type eutectic solvent according to claim 1, characterized in that: in the step 1), the molar ratio of the polyethylene glycol 200 to the thiourea is 5:1 to 1:1, and the specific molar ratio of the polyethylene glycol 200 to the thiourea is 2: 1.
3. The method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea type eutectic solvent according to claim 1, characterized in that: in step 1), the temperature of the eutectic solvent is 20 to 90 ℃ and the time is 4 to 12 hours.
4. The method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea type eutectic solvent according to claim 4, characterized in that: in the step 1), the formation temperature of the eutectic solvent is 30 ℃ and the time is 8 hours.
5. The method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea type eutectic solvent according to claim 1, characterized in that: in step 3), the mass ratio of the eutectic solvent to the mixed powder containing lithium cobaltate is 100:1 to 10:1, specifically, the mass ratio of the eutectic solvent to the mixed powder containing lithium cobaltate is 50: 1.
6. The method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea type eutectic solvent according to claim 1, characterized in that: in step 3), the temperature of the eutectic solvent during the dissolution of the mixed powder containing lithium cobaltate is 30 to 100 degrees celsius, and the dissolution time is 0.1 to 48 hours.
7. The method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea type eutectic solvent according to claim 1, characterized in that: in step 3), the temperature of the eutectic solvent during the dissolution of the mixed powder containing lithium cobaltate is 80 degrees celsius, and the dissolution time is 12 hours.
8. The method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea type eutectic solvent according to claim 1, characterized in that: in step 4), step 6), the centrifugation rate was 10000 rpm and the centrifugation time was 10 minutes.
9. The method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea type eutectic solvent according to claim 1, characterized in that: in step 5), the process of measuring the dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent needs to be repeated three times, and the average value of the three measured concentrations is taken as the final dissolved concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent.
10. The method for dissolving and extracting lithium cobaltate by using the polyglycol/thiourea type eutectic solvent according to claim 1, characterized in that: in the step 5), after the dissolution concentrations of lithium cobaltate and cobalt ions in the lithium cobaltate extraction solvent are measured to reach the standard, the operation of the step 6) is carried out; the standard of the dissolution concentration of lithium cobaltate in the lithium cobaltate extraction solvent is as follows: the PPM concentration of cobalt ions in the lithium cobaltate extraction solvent is greater than or equal to 1200 and the PPM concentration of lithium cobaltate in the lithium cobaltate extraction solvent is greater than or equal to 2000.
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