METHOD FOR RECYCLING BATTERY BY INCOMPLETE EXTRACTION

Abstract

Disclosed is an incomplete extraction method for recycling batteries, which may include: introducing a pretreatment gas into a device loaded with a waste battery powder, and bringing a gas outlet into communication with absorption liquid A and absorption liquid B in order; raising the temperature and introducing the pretreatment gas; reducing the temperature and introducing a reaction gas; raising the temperature, introducing the reaction gas, and then introducing the pretreatment gas; and reducing the temperature, and turning off the pretreatment gas; adding an extractant to absorption liquid A, mixing the mixture, taking organic phase A, adding a stripping agent, and taking aqueous phase A; and adjusting the pH to acidity, then adding an extractant, taking organic phase B, adding a stripping agent to obtain a stock solution enriched in Li, Mn, Ni and Co.

Claims

1. A method for recycling a battery by incomplete extraction, characterized by comprising: (1) subjecting waste batteries to discharging, crushing, and pyrolysis to obtain a waste battery powder; (2) introducing a pretreatment gas into a device loaded with the waste battery powder, and bringing a gas outlet of the device into communication with absorption liquid A and absorption liquid B in order; (3) raising the temperature and continuing to introduce the pretreatment gas; reducing the temperature and introducing a reaction gas; raising the temperature, introducing the reaction gas, and then introducing the pretreatment gas; and reducing the temperature, and turning off the pretreatment gas; (4) adding an extractant to absorption liquid A, mixing the mixture, carrying out liquid separation, taking organic phase A, adding a stripping agent for liquid separation, and taking aqueous phase A; and (5) adjusting the pH of aqueous phase A to acidity, then adding an extractant for liquid separation, taking organic phase B, adding a stripping agent for liquid separation to obtain a stock solution enriched in Li, Mn, Ni and Co; wherein the pretreatment gas is at least one of nitrogen, helium, argon or neon; the reaction gas is one of chlorine gas, fluorine gas or bromine gas; absorption liquid A is an acid solution, the acid solution is HCl; and absorption liquid B is an alkaline solution, the alkaline solution is a NaOH or KOH solution; the extractant is at least one of [(CH.sub.3).sub.3C(CH.sub.2).sub.5CH(CH.sub.3)CH.sub.2]HPO.sub.2 and [CH.sub.3(CH.sub.2).sub.4CH(CH.sub.3)CH.sub.2].sub.2HPO.sub.2; and the stripping agent is at least one of diethylenetriamine pentaacetic acid and triethylenetetraamine hexaacetic acid.

2. The method of claim 1, wherein, in step (2), the introduced pretreatment gas has a flow rate of 10-30 mL/min and a temperature of 20-40° C.

3. (canceled)

4. (canceled)

5. The method of claim 1, wherein, the specific operation of step (3) involves: raising the temperature to 300-400° C. at a ramp rate of 3-5° C./min, maintaining the flow rate, continuing to introduce the pretreatment gas for 20-60 min, and maintaining the gas flow rate; reducing the temperature to 20-40° C. and then introducing the reaction gas at a flow rate of 10-50 mL/min; raising the temperature to 200-240° C. at a ramp rate of 3-5° C./min, maintaining the temperature and introducing the reaction gas for 1-3 h; raising the temperature to 280-320° C. at a ramp rate of 3-5° C./min, maintaining the temperature and introducing the reaction gas for 2-3 h; further raising the temperature to 360-380° C. at a ramp rate of 3-5° C./min, maintaining the temperature and introducing the reaction gas for 1-3 h; and finally raising the temperature to 450-470° C. at a ramp rate of 3-5° C./min, maintaining the temperature, introducing the reaction gas for 2-4 h, turning off the reaction gas, introducing the pretreatment gas, and reducing the temperature to 20-35° C.

6. (canceled)

7. (canceled)

8. The method of claim 1, wherein, in step (4), the volume ratio of absorption liquid A to the extractant is 1 : (1-5); and in step (4), the volume ratio of organic phase A to the stripping agent is 1:(1-5).

9. The method of claim 1, wherein, in step (5), the volume ratio of organic phase B to the stripping agent is 1:(1-5).

10. Use of the method of claim 1 in metal recovery.

Description

DETAILED DESCRIPTION

[0034] In order to understand the present disclosure in depth, preferred experimental schemes of the present disclosure will be described below in conjunction with examples to further illustrate the characteristics and advantages of the present disclosure. Any variations or changes that do not deviate from the gist of the present disclosure can be understood by those skilled in the art. The scope of protection of the present disclosure is determined by the scope of the claims.

Embodiment 1

[0035] A method for recycling a battery by incomplete extraction was involved, comprising the following specific steps: [0036] (1) subjecting waste batteries to discharge, coarse crushing, pyrolysis and fine crushing in order to obtain a waste battery powder; [0037] (2) placing the waste battery powder in a closed tube furnace, introducing nitrogen with a specification of 99.999% for 10 min at a flow rate of 10 mL/min at 20° C., connecting a gas outlet to tail gas absorption apparatus A in which a 0.1 mol/L HCl solution was placed inside as an absorption liquid, and connecting tail gas absorption apparatus A to tail gas absorption apparatus B in which a 0.5 mol/L NaOH solution was placed inside as an absorption liquid; [0038] (3) raising the temperature to 300° C. at a ramp rate of 5° C./min, maintaining the flow rate, continuing to introduce a pretreatment gas for 20 min, and maintaining the gas flow rate; when the temperature was about to reach 20° C., introducing chlorine gas with a specification of 99.999% at a flow rate of 10 mL/min; raising the temperature to 200° C. at a ramp rate of 5° C./min, maintaining the temperature and introducing chlorine gas for 1 h; raising the temperature to 280° C. at a ramp rate of 5° C./min, maintaining the temperature and introducing chlorine gas for 2 h; raising the temperature to 360° C. at a ramp rate of 5° C./min, maintaining the temperature and introducing chlorine gas for 1 h; finally raising the temperature to 450° C. at a ramp rate of 5° C./min, maintaining the temperature, introducing chlorine gas for 2 h; and after the reaction was completed, turning off the chlorine gas, introducing the pretreatment gas, and reducing the temperature to ambient temperature; [0039] (4) after the temperature dropped to ambient temperature, turning off the pretreatment gas, placing absorption liquid A enriched in Li, Mn, Ni and Co in an extraction apparatus, adding [(CH.sub.3).sub.3C(CH.sub.2).sub.5CH(CH.sub.3)CH.sub.2]HPO.sub.2 at a volume ratio of 1:1, shaking the mixture for 15 min for liquid separation, adding diethylenetriamine pentaacetic acid (DTPA) to organic phase A at a volume ratio of 1:1, and shaking the mixture for 15 min for liquid separation to obtain aqueous phase A; and [0040] (5) adjusting the pH value of aqueous phase A to 2.8 with 0.1 mol/L HCl, adding [CH.sub.3(CH.sub.2).sub.4CH(CH.sub.3)CH.sub.2].sub.2HPO.sub.2 at a volume ratio of 1:1, shaking the mixture for 15 min for liquid separation, adding triethylenetetraamine hexaacetic acid (TTHA) to organic phase B at a volume ratio of 1:1, shaking the mixture for 15 min for liquid separation, adjusting the pH value of aqueous phase B to 4.2 with 0.1 mol/L HCl, wherein aqueous phase B was a stock solution enriched in Li, Mn, Ni and Co, concentrating and crystallizing aqueous phase B to obtain a precursor material, and further sintering the precursor material to form a ternary positive electrode material.

Embodiment 2

[0041] A method for recycling a battery by incomplete extraction was involved, comprising the following specific steps: [0042] (1) subjecting waste batteries to discharge, coarse crushing, pyrolysis and fine crushing in order to obtain a waste battery powder; [0043] (2) placing the waste battery powder in a closed tube furnace, introducing helium with a specification of 99.999% for 20 min at a flow rate of 20 mL/min at 30° C., connecting a gas outlet to tail gas absorption plant A in which a 0.2 mol/L HCl solution was placed inside as an absorption liquid, and connecting tail gas absorption plant A to tail gas absorption apparatus B in which a 0.7 mol/L KOH solution was placed inside as an absorption liquid; [0044] (3) raising the temperature to 350° C. at a ramp rate of 5° C./min, maintaining the flow rate, continuing to introduce a pretreatment gas for 40 min, and maintaining the gas flow rate; after the temperature was reduced to 30° C., introducing chlorine gas with a specification of 99.999% at a flow rate of 30 mL/min; raising the temperature to 220° C. at a ramp rate of 5° C./min, maintaining the temperature and introducing chlorine gas for 2 h; further raising the temperature to 300° C. at a ramp rate of 5° C./min, maintaining the temperature and introducing chlorine gas for 2.5 h; raising the temperature to 370° C. at a ramp rate of 5° C./min, maintaining the temperature and introducing chlorine gas for 2 h; finally raising the temperature to 460° C. at a ramp rate of 5° C./min, maintaining the temperature, introducing chlorine gas for 3 h; and turning off the chlorine gas, introducing the pretreatment gas, and reducing the temperature to ambient temperature; [0045] (4) after the temperature dropped to ambient temperature, turning off the pretreatment gas, placing absorption liquid A enriched in Li, Mn, Ni and Co in an extraction apparatus, adding [(CH.sub.3).sub.3C(CH.sub.2).sub.5CH(CH.sub.3)CH.sub.2]HPO.sub.2 at a volume ratio 1:1, shaking the mixture for 15 min for liquid separation, adding diethylenetriamine pentaacetic acid (DTPA) to organic phase A at a volume ratio 1:1, and shaking the mixture for 15 min for liquid separation to obtain aqueous phase A; and [0046] (5) adjusting the pH value of aqueous phase A to 2.8 with 0.1 mol/L HCl, adding [CH3(CH2)4CH(CH3)CH2]2HPO2 at a volume ratio of 1:1, shaking the mixture for 15 min for liquid separation, adding triethylenetetraamine hexaacetic acid (TTHA) to organic phase B at a volume ratio of 1:1, shaking the mixture for 15 min for liquid separation, adjusting the pH value of aqueous phase B to 4.2 with 0.1 mol/L HCl, wherein aqueous phase B was a stock solution enriched in Li, Mn, Ni and Co, concentrating and crystallizing aqueous phase B to obtain a precursor material, and further sintering the precursor material to form a ternary positive electrode material.

Embodiment 3

[0047] A method for recycling a battery by incomplete extraction was involved, comprising the following specific steps: [0048] (1) subjecting waste batteries to discharge, coarse crushing, pyrolysis and fine crushing in order to obtain a waste battery powder; [0049] (2) placing the waste battery powder in a tube furnace, closing the tube furnace, introducing argon with a specification of 99.999% for 30 min at a flow rate of 30 mL/min at 40° C., connecting a gas outlet to tail gas absorption plant A in which a 0.3 mol/L HCl solution was placed inside as an absorption liquid, and connecting tail gas absorption plant A to tail gas absorption apparatus B in which a 1 mol/L KOH solution was placed inside as an absorption liquid; [0050] (3) raising the temperature to 400° C. at a ramp rate of 5° C./min, maintaining the flow rate, continuing to introduce a pretreatment gas for 60 min, and maintaining the gas flow rate; when the temperature was about to reach 40° C., introducing chlorine gas with a specification of 99.999% at a flow rate of 50 mL/min; raising the temperature to 240° C. at a ramp rate of 5° C./min, maintaining the temperature and introducing chlorine gas for 3 h; then raising the temperature to 320° C. at a ramp rate of 5° C./min, maintaining the temperature and introducing chlorine gas for 3 h; subsequently, raising the temperature to 380° C. at a ramp rate of 5° C./min, maintaining the temperature and introducing chlorine gas for 3 h; finally raising the temperature to 470° C. at a ramp rate of 5° C./min, maintaining the temperature, introducing chlorine gas for 4 h; and turning off the chlorine gas, introducing the pretreatment gas, and reducing the temperature to ambient temperature; [0051] (4) after the temperature dropped to ambient temperature, turning off the pretreatment gas, placing absorption liquid A enriched in Li, Mn, Ni and Co in an extraction apparatus, adding (CH.sub.3).sub.3C(CH.sub.2).sub.5CH(CH.sub.3)CH.sub.2]HPO.sub.2 at a volume ratio 1:5, shaking the mixture for 25 min for liquid separation, adding diethylenetriamine pentaacetic acid (DTPA) to organic phase A at a volume ratio 1:5, and shaking the mixture for 25 min for liquid separation to obtain aqueous phase A; and [0052] (5) adjusting the pH value of aqueous phase A to 6.2 with 0.1 mol/L HCl, adding [CH.sub.3(CH.sub.2).sub.4CH(CH.sub.3)CH.sub.2].sub.2HPO.sub.2 at a volume ratio of 1:3, shaking the mixture for 25 min for liquid separation, adding triethylenetetraamine hexaacetic acid (TTHA) to organic phase B at a volume ratio of 1:5, shaking the mixture for 25 min for liquid separation, adjusting the pH value of aqueous phase B to 6.8 with 0.1 mol/L HCl, wherein aqueous phase B was a stock solution enriched in Li, Mn, Ni and Co, concentrating and crystallizing aqueous phase B to obtain a precursor material, and further sintering the precursor material to form a ternary positive electrode material.

COMPARATIVE EXAMPLE

[0053] A method for recycling batteries was involved, comprising the following steps: [0054] (1) subjecting waste lithium-ion batteries to discharging, crushing, pyrolysis, and crushing to form a battery waste material; [0055] (2) leaching the battery waste material with sulfuric acid, adding copper to remove iron, and adding sodium carbonate to remove iron and aluminum; [0056] (3) performing filtration, extracting the filtrate with P204, back-extracting the organic phase with sulfuric acid, and adding sodium carbonate to precipitate lithium; and [0057] (4) extracting nickel from the raffinate with a P507 extractant, wherein the aqueous phase was an Ni solution, and back-extracting the organic phase with hydrochloric acid to obtain a Co solution.

[0058] Comparison Results:

[0059] Table 1 was the results of the recovery rates of the four elements, lithium, nickel, cobalt and manganese, in the stock solutions obtained in Embodiments 1, 2 and 3 and Comparative Example 1.

TABLE-US-00001 TABLE 1 Recovery rates of the four elements, lithium, nickel, cobalt and manganese, in the stock solutions (%) Main Embodi- Embodi- Embodi- Comparative elements ment 1 ment 2 ment 3 Example Li amount 99.87 99.93 99.89 89.83 Ni amount 99.91 99.95 99.92 89.74 Co amount 99.85 99.98 99.94 89.64 Mn amount 99.90 99.91 99.88 89.34

[0060] It can be seen from Table 1 that the recovery rates of the four elements, lithium, nickel, cobalt and manganese, in Embodiments 1-3 were all higher than those of the comparative example, and Embodiment 2 had the best recovery effects.

[0061] Table 2 was the results of the concentrations of impurity elements as measured by ICP-OES for the stock solutions obtained in Embodiments 1, 2 and 3 and Comparative Example 1.

TABLE-US-00002 TABLE 2 Content of impurities in stock solution (%) Impurity Embodi- Embodi- Embodi- Comparative element ment 1 ment 2 ment 3 Example Fe 0.0008 0.0005 0.0006 0.05 Al 0.006 0.001 0.007 0.01 Cu 0.001 0.0008 0.001 0.004 Zn 0.0009 0.0007 0.0008 0.008 Pb 0.0009 0.0007 0.0008 0.0008 Cd 0.0003 0.0002 0.0003 0.006 K 0.009 0.008 0.008 0.008 Na 0.004 0.003 0.003 0.09 Ca 0.008 0.005 0.006 0.03 Mg 0.005 0.003 0.004 0.03 Insolubles 0.007 0.003 0.005 0.01

[0062] It can be seen from Table 2 that the contents of impurities in the stock solutions of Embodiments 1-3 are significantly lower than the contents of impurities in the stock solution of Comparative Example 1 obtained by the extraction method, indicating that the use of the incomplete extraction method for recycling batteries of the present disclosure results in better metal recovery effects.

[0063] Table 3 is the energy consumptions, water amounts and extractant amounts for 1 ton of the stock solutions obtained in Embodiments 1, 2 and 3 and Comparative Example 1 with the same concentration.

TABLE-US-00003 TABLE 3 Resource consumption for producing 1 ton of stock solution Embodi- Embodi- Embodi- Comparative Impurity ment 1 ment 2 ment 3 Example Energy 14 18 24 43 consumption/ kWh Water amount/t 1.2 1.3 1.3 1.6 Total extractant 2 5 8 13 amount/t

[0064] It can be seen from Table 3 that the energy consumptions and extractant amounts of Embodiments 1, 2 and 3 are significantly lower than those of Comparative Example 1 which uses the extraction method, and therefore, the use of the incomplete extraction method for recycling batteries of the present disclosure in metal recovery results in a low cost and a high profit.

[0065] The above-mentioned embodiments are preferred embodiments of the present disclosure; however, the embodiments of the present disclosure are not limited by the above-mentioned embodiments. Any other changes, modifications, and simplifications made without departing from the spirit and principle of the present disclosure should be equivalent replacement modes, and are all included in the scope of protection of the present disclosure.