CN113809426A - Discharging method of waste lithium ion battery - Google Patents
Discharging method of waste lithium ion battery Download PDFInfo
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- CN113809426A CN113809426A CN202111093831.4A CN202111093831A CN113809426A CN 113809426 A CN113809426 A CN 113809426A CN 202111093831 A CN202111093831 A CN 202111093831A CN 113809426 A CN113809426 A CN 113809426A
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- 239000002699 waste material Substances 0.000 title claims abstract description 101
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000007599 discharging Methods 0.000 title claims abstract description 59
- 208000028659 discharge Diseases 0.000 claims abstract description 82
- 239000000178 monomer Substances 0.000 claims abstract description 62
- 239000012266 salt solution Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 13
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 12
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000011686 zinc sulphate Substances 0.000 claims abstract description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 4
- 230000008878 coupling Effects 0.000 claims description 10
- 238000010168 coupling process Methods 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 28
- 239000000243 solution Substances 0.000 description 44
- 239000010926 waste battery Substances 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 22
- 239000002184 metal Substances 0.000 description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 238000001514 detection method Methods 0.000 description 9
- 238000012935 Averaging Methods 0.000 description 6
- 239000007832 Na2SO4 Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a discharging method of a waste lithium ion battery, which comprises the following steps: (1) disassembling the waste power battery pack into waste lithium ion battery monomers; (2) measuring the pressure of the waste lithium ion battery monomer in the step (1), and separating the waste lithium ion battery monomer needing to be discharged to obtain the waste lithium ion battery monomer needing to be subjected to discharge treatment; (3) putting a waste lithium ion battery monomer needing discharge treatment into a container filled with a salt solution, adding solid conductive powder into the container filled with the salt solution, and applying an external physical field to perform discharge operation to obtain a discharged waste lithium ion battery; the salt solution is CuSO4、FeSO4、ZnSO4、NiSO4、CoSO4One or more of the above, the salt solution has a concentration of 5% -50%, a temperature of 25-35 deg.C, and a pH of 7-10. The invention can shorten the discharge time and improve the discharge effect.
Description
Technical Field
The invention belongs to the field of waste lithium ion battery recovery, and particularly relates to a discharge method of a waste lithium ion battery.
Background
With the rapid development of modern technology, the pollution problem of social energy and environment ecology becomes more and more prominent, and the pollution problem of various waste batteries to the environment and the ecology becomes the focus of social attention. The nickel cobalt lithium manganate ion battery is widely applied to power batteries and energy storage batteries due to the characteristics of high capacity, stable cycle performance, high working platform voltage and the like, and the requirements of the power batteries and the energy storage batteries on battery materials are generally greater than those of conventional small batteries. Therefore, a large amount of waste lithium ion batteries are scrapped in the future 3-5 years, and the recycling of the waste lithium ion batteries has high social value.
However, a considerable portion of the voltage remains in the used lithium ion battery, and the discharge operation must be performed to reduce the remaining voltage to within a safe range in order to ensure safety of personnel and equipment. At present, no independent discharge research on the waste lithium ion batteries is reported in China, the recovery focus of the waste lithium ion batteries is mainly focused on the recovery of products at the rear section, the focus of the discharge treatment at the front section is low, and the discharge operation is generally carried out by adopting 5-10% NaCl solution at present. For example, in the "efficient recovery and separation process based on lithium ion batteries in waste mobile phones" published in chinese patent CN 106558739 a, discharge operation is performed before crushing and disassembling the batteries, and 10% NaCl salt solution is used for soaking for 48 hours until the residual voltage of the batteries meets the requirement of safe disassembly. The residual voltage of the waste battery can meet the requirement of safe disassembly by adopting 5-10% NaCl salt solution to carry out battery discharge operation, but the discharge rate is slow, the residual voltage is reduced to below 1V by soaking for more than 24h generally, and chloride ions which are difficult to remove are introduced into leachateAnd influence is brought to the subsequent impurity removal purification and product recovery stages. As another example, CN 104538695A discloses a method for recovering metals from waste lithium nickel cobalt manganese oxide batteries and preparing lithium nickel cobalt manganese oxide, wherein 0.1-1mol/L NaOH solution is used to perform discharge operation on the batteries at room temperature for 1-3h before the batteries are broken and disassembled, OH is added-In aqueous solution to Cl-More difficult discharge adopts the NaOH solution and will reduce the discharge rate and the discharge effect of battery certainly, and NaOH can cause the corruption to the aluminum hull and lead to revealing of electrolyte to pollute quality of water when handling laminate polymer battery.
In summary, in the conventional lithium ion recovery discharge process, a long discharge time (generally over 24 hours) is still common, the discharge effect is not ideal, the discharge can only be about 0.7V, and in the treatment process, the battery pack is easy to corrode, so that a highly toxic electrolyte leaks into a discharge system, which is very harmful to personnel and environment safety.
Disclosure of Invention
In order to solve the technical problems of long discharge time, unsatisfactory discharge effect and the like of the conventional discharge method for recycling the lithium ion battery, the invention provides an efficient clean discharge method for the waste lithium ion battery, and aims to shorten the discharge time and improve the discharge effect.
The invention adopts the following technical scheme:
a discharge method of a waste lithium ion battery is characterized by comprising the following steps:
(1) disassembling the waste power battery pack into waste lithium ion battery monomers;
(2) measuring the pressure of the waste lithium ion battery monomer in the step (1), and separating the waste lithium ion battery monomer needing to be discharged to obtain the waste lithium ion battery monomer needing to be subjected to discharge treatment;
(3) putting a waste lithium ion battery monomer needing discharge treatment into a container filled with a salt solution, adding solid conductive powder into the container filled with the salt solution, and applying an external physical field to perform discharge operation to obtain a discharged waste lithium ion battery; the salt solution is CuSO4、FeSO4、ZnSO4、NiSO4、CoSO4One or more of the above, the salt solution has a concentration of 5% -50%, a temperature of 25-35 deg.C, and a pH of 7-10; the addition amount of the solid conductive powder is 1-10% of the mass of the salt solution.
The discharge method of the waste lithium ion battery is characterized in that the external physical field applied in the step (3) is one of an ultrasonic field, a flow field and a coupling field of the ultrasonic field and the flow field; when the applied external physical field is one of an ultrasonic field and a coupling field of the ultrasonic field and the flow field, the ultrasonic field is applied through an ultrasonic generating device, and the rated power applied by the ultrasonic field is 30W-100W; when the applied external physical field is one of a flow field, an ultrasonic field and a coupling field of the flow field, the flow field is applied in a mechanical stirring mode, and the rotating speed of the mechanical stirring is 200-500 rpm.
The discharging method of the waste lithium ion battery is characterized in that the concentration of the salt solution in the step (3) is 5% -20%.
The discharging method of the waste lithium ion battery is characterized in that the concentration of the salt solution in the step (3) is 10% -15%.
The discharging method of the waste lithium ion battery is characterized in that the pH value of the salt solution in the step (3) is 7-8.
The discharge method of the waste lithium ion battery is characterized in that in the step (3), the solid conductive powder is at least one of iron powder, zinc powder and copper powder.
The discharging method of the waste lithium ion battery is characterized in that in the step (3), the addition amount of the solid conductive powder is 2-5% of the mass of the salt solution; and (4) the time that the voltage of the discharged waste lithium ion battery in the step (3) is lower than 1V is not higher than 12 h.
The discharge method of the waste lithium ion battery is characterized in that the waste lithium ion battery is one or more of a waste ternary power battery, a lithium cobaltate battery, a lithium manganate battery, a lithium nickelate battery and a lithium iron phosphate battery.
The discharging method of the waste lithium ion batteries is characterized in that the residual voltages of the waste power battery pack and the waste lithium ion battery monomer in the step (1) are not lower than 1V.
The discharging method of the waste lithium ion batteries is characterized in that the residual voltages of the waste power battery pack and the waste lithium ion battery monomer in the step (1) are 3.8V-3.85V.
The invention has the beneficial technical effects that: 1) the discharge operation is carried out before the disassembly of the waste lithium ion battery, so that potential safety hazards brought to subsequent recovery treatment are avoided, the residual voltage of the waste lithium ion battery can be rapidly and safely detected and monitored by adopting the conventional equipment, and the continuous discharge operation is realized without potential safety hazards; 2) the invention firstly provides a technology for realizing solid-liquid common discharge by mixing substances such as zinc sulfate solution and the like, conductive powder and an external physical field, and avoids the use of a main discharge medium NaCl salt solution, so that no chloride ion is introduced, the generation of harmful gas chlorine is avoided, the subsequent production is not influenced, and the high-efficiency continuous clean discharge of the waste lithium ion battery can be realized; 3) the method has the advantages that substances such as zinc sulfate solution and the like, conductive powder and an external physical field solid-liquid cooperative discharging technology are adopted, so that the damage to the battery shell is avoided in the discharging process of the waste battery, and the leakage of electrolyte caused by the corrosion of other discharging media such as sodium hydroxide and sodium chloride solution to the battery shell is avoided to pollute the water quality; 4) the method is suitable for continuous operation, does not produce secondary pollution, has environmental protection and economic benefit, has simple process and low production cost, and is suitable for large-scale industrial production; 5) by adopting the method, the technical defect that the existing method can not completely discharge is overcome, and the residual voltage after discharge treatment can be reduced to 0V; 6) the method can obviously shorten the discharge time, and the time for discharging to 0V can be shortened to 8 h. Discharging is carried out in the salt solution, and the discharge of the residual electric quantity of the waste lithium ion battery is realized through the synergistic effect of the oxidation-reduction reaction and the external physical field. The method can realize high-efficiency discharge, obviously shortens the discharge time, is favorable for achieving thorough discharge (discharge to 0V), and has obvious advantages compared with the existing method which can only achieve the discharge effect of 0.7V. In addition, the method of the invention does not corrode the battery pack (or single battery) device, does not cause leakage of highly toxic electrolyte (such as methyl carboxylate) in the discharging process, and does not cause adverse effects on personnel and environment.
Drawings
FIG. 1 is a graph illustrating the discharge effect of a battery according to various embodiments of the present invention;
FIG. 2 is a graph showing the effect of discharging a battery in a comparative example of the present invention.
Detailed Description
The invention relates to a discharge method of waste lithium ion batteries, which comprises the steps of placing a battery pack of the waste lithium ion batteries or a waste lithium ion battery monomer obtained by disassembly into an aqueous solution dissolved with metal salt for discharging, wherein the metal salt is prior to H in the aqueous solution+Obtaining electrons; the solution in which the metal salt is dissolved is preferably an aqueous solution of a metal sulfate, and the solution system is allowed to contain some solvent other than water, preferably a solvent infinitely miscible with water. The discharging method specifically comprises the following steps:
(1) disassembling the waste power battery pack into waste lithium ion battery monomers; the residual voltage of the waste power battery pack and the waste lithium ion battery monomer is not lower than 1V, and preferably, the residual voltage of the waste power battery pack and the waste lithium ion battery monomer is 3.8V-3.85V. The waste lithium ion battery is one or more of a waste ternary power battery, a lithium cobaltate battery, a lithium manganate battery, a lithium nickelate battery and a lithium iron phosphate battery.
(2) Measuring the pressure of the waste lithium ion battery monomer in the step (1), and quickly and continuously separating the waste lithium ion battery monomer needing to be discharged by using the conventional equipment to obtain the waste lithium ion battery monomer needing to be discharged;
(3) putting the waste lithium ion battery monomer needing discharge treatment into a container filled with a salt solution, adding solid conductive powder into the container filled with the salt solution, applying an external physical field to enhance the discharge effect and carrying out discharge operation to obtain discharged waste lithium ionsA sub-battery; and the time that the voltage of the discharged waste lithium ion battery is lower than 1V is not higher than 12 h. The solution dissolved with the metal salt contains the conductive material, and the conductive material is added into the solution dissolved with the metal salt in the discharging process, so that the discharging effect can be further improved, and the discharging efficiency can be improved. The salt solution is water-soluble CuSO4、FeSO4、ZnSO4、NiSO4、CoSO4Most preferably, the metal salt is ZnSO4The zinc sulfate solution is adopted for discharging, the effect is better, the discharging time is shorter, the discharging effect (discharging degree) can reach 0V easily, and the zinc sulfate solution has a better discharging effect. The concentration of the solution system dissolved with the metal sulfate is 5-50%, the temperature is 25-35 ℃, and the pH value is 7-10; in the discharging process, the temperature of the solution dissolved with the metal salt is controlled to be 25-35 ℃, and the discharging efficiency can be further improved and the discharging effect can be further improved by controlling the temperature at the discharging temperature. The mass percentage of the metal sulfate in the solution system dissolved with the metal sulfate is controlled, so that the discharge efficiency is further improved, and the discharge effect is further improved; preferably, the concentration of the metal sulfate in the solution in which the metal salt is dissolved is 5% to 50%, and at this preferred concentration, the discharge can be made to 0V in 12 hours, and the technical effect is excellent. Preferably, the concentration of the solution system dissolved with the metal sulfate is 5% -20%, further, the concentration of the solution system dissolved with the metal sulfate is 10% -15%, and the time of discharging to 0V can be shortened to 8h when the concentration of the solution system dissolved with the metal sulfate is 10% -15%, so that the discharging effect is better, and the discharging efficiency is better. In the discharging process, the operations of controlling the pH value in the discharging process, controlling the temperature in the discharging process, adding a conductive material in the solution dissolved with the reducing salt and the like can further improve the discharging effect, shorten the discharging time and improve the discharging effect. The pH value of the solution system dissolved with the metal sulfate is 7-10, and the pH value is the initial pH value of the solution dissolved with the metal salt; preferably, the pH of the solution system in which the metal sulfate is dissolved is 7 to 8, and preferably, the pH of the solution system in which the metal sulfate is dissolved is 7 to 7.5. The solid conductive powder is at least one of iron powder, zinc powder and copper powder, and the addition amount of the solid conductive powder is the mass of the salt solution1% -10%, preferably, the addition amount of the solid conductive powder is 2% -5% of the mass of the salt solution. The applied external physical field is one of an ultrasonic field, a flow field and a coupling field of the ultrasonic field and the flow field, when the applied external physical field is one of the ultrasonic field, the coupling field of the ultrasonic field and the flow field, the ultrasonic field is applied through an ultrasonic generating device, and the rated power applied by the ultrasonic field is 30W-100W; when the applied external physical field is one of a flow field, an ultrasonic field and a coupling field of the flow field, the flow field is applied in a mechanical stirring mode, and the rotating speed of the mechanical stirring is 200-500 rpm.
And recording and detecting the residual voltage of the battery in the corresponding solution at different time points until the residual voltage is below 1V, and comparing the time and the discharge effect required by discharging to a safe potential under different salt solutions.
The invention utilizes the simple electrolysis principle to release electrons from the anode and the cathode to obtain electrons, and strengthens the process by applying an external physical field. The application of an ultrasonic field, a flow field or a coupling field of the ultrasonic field and the flow field can realize the rapid reduction of the residual pressure of the waste lithium ion battery in the discharging process. By using a catalyst of H+The obtained solution of the electronic metal sulfate is used as a discharge medium to replace a 5-10% NaCl solution which is mainly adopted at present, so that the introduction of chloride ions is avoided, and the high-efficiency clean discharge of the waste lithium ion battery can be realized.
The following are exemplary embodiments of the present invention, but it should be understood that the scope of the present invention is not limited to these embodiments. The percentages in the following examples, unless otherwise stated, are by weight. In the following examples and comparative examples, the waste power battery is a waste 523 type ternary lithium battery.
Example 1
The method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into battery monomers, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each battery monomer, and separating the battery monomers with the residual voltage higher than 1V to enter a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in ZnSO with 5 percent4In an open container of the solution, adjusting the pH value of the solution to 7-7.5 and the temperature to 25 ℃, applying an ultrasonic field and a flow field, and measuring once every 1hResidual voltage of 5 cells was averaged and recorded until discharge was complete. At the moment, the residual voltage of the waste battery is reduced to 0V after the waste battery is soaked for 12 hours. The battery discharge effect is shown in figure 1.
Example 2
The method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into battery monomers, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each battery monomer, and separating the battery monomers with the residual voltage higher than 1V to enter a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in ZnSO with 5 percent4In an open container of the solution, adjusting the pH value of the solution to 7-7.5 and the temperature to 30 ℃, applying an ultrasonic field and a flow field, measuring the residual voltage of 5 groups of batteries every 1 hour, averaging and recording until the discharge is complete. At the moment, the residual voltage of the waste battery is reduced to 0V after the waste battery is soaked for 10 hours.
Example 3
The method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into battery monomers, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each battery monomer, and separating the battery monomers with the residual voltage higher than 1V to enter a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in ZnSO with 10 percent of residual voltage4In an open container of the solution, adjusting the pH value of the solution to 7-7.5 and the temperature to 30 ℃, applying an ultrasonic field and a flow field, measuring the residual voltage of 5 groups of batteries every 1 hour, averaging and recording until the discharge is complete. At the moment, the residual voltage of the waste battery is reduced to 0V after the waste battery is soaked for 8 hours. The battery discharge effect is shown in figure 1.
Example 4
The method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into battery monomers, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each battery monomer, and separating the battery monomers with the residual voltage higher than 1V to enter a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in ZnSO with 10 percent of residual voltage4In an open container of the solution, adjusting the pH value of the solution to 7-7.5 and the temperature to 30 ℃, and then adding 2% of zincAnd applying an ultrasonic field and a flow field, measuring the residual voltage of 5 groups of batteries every 1h, averaging and recording until the discharge is complete. At the moment, the residual voltage of the waste battery is reduced to 0V after the waste battery is soaked for 6 hours. The discharge efficiency of the waste battery can be further accelerated by adopting a solid-liquid combined discharge mode.
Comparative example 1
This comparative example discusses the use of Na2SO4Substitution of ZnSO4The method comprises the following steps: the method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into battery monomers, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each battery monomer, and separating the battery monomers with the residual voltage higher than 1V to enter a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in 5 percent of Na2SO4In an open container of the solution, adjusting the pH value of the solution to 7-7.5 and the temperature to 25 ℃, applying an ultrasonic field and a flow field, measuring the residual voltage of 5 groups of batteries every 1 hour, averaging and recording until the discharge is complete. At this time, the residual voltage of the waste battery after soaking for 24 hours is 1.4V. The battery discharge effect is shown in fig. 2.
Comparative example 2
This comparative example discusses the use of Na2SO4Substitution of ZnSO4And discharged at 30 ℃ as follows: the method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into battery monomers, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each battery monomer, and separating the battery monomers with the residual voltage higher than 1V to enter a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in 5 percent of Na2SO4In an open container of the solution, adjusting the pH value of the solution to 7-7.5 and the temperature to 30 ℃, applying an ultrasonic field and a flow field, measuring the residual voltage of 5 groups of batteries every 1 hour, averaging and recording until the discharge is complete. At this time, the residual voltage of the waste battery after soaking for 24 hours is about 1.3V. The battery discharge effect is shown in fig. 2.
Comparative example 3
This comparative example discusses the use of Na2SO4Replacing said ZnSO4And discharged at 10% concentration as follows: the method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into battery monomers, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each battery monomer, and separating the battery monomers with the residual voltage higher than 1V to enter a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in 10 percent of Na2SO4In an open container of the solution, adjusting the pH value of the solution to 7-7.5 and the temperature to 30 ℃, applying an ultrasonic field and a flow field, measuring the residual voltage of 5 groups of batteries every 1 hour, averaging and recording until the discharge is complete. At this time, the residual voltage of the waste battery after soaking for 24 hours is about 1.1V. The battery discharge effect is shown in fig. 2.
Comparative example 4
This comparative example discusses the use of conventional NaCl discharge, as follows: the method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into battery monomers, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each battery monomer, and separating the battery monomers with the residual voltage higher than 1V to enter a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in an open container filled with 5% NaCl solution, the pH value of the solution is adjusted to 7-7.5, the temperature is 30 ℃, an ultrasonic field and a flow field are applied, the residual voltage of the 5 groups of batteries is measured every 1 hour, and the average value is taken and recorded until the discharge is complete. At this time, the residual voltage of the waste battery after soaking for 24 hours is 0.7V. The battery discharge effect is shown in figure 1.
Comparative example 5
Blank control: the method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into battery monomers, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each battery monomer, and separating the battery monomers with the residual voltage higher than 1V to enter a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in an open container filled with pure water, the pH value of the solution is adjusted to 7-7.5, the temperature is 30 ℃, an ultrasonic field and a flow field are applied, the residual voltage of the 5 groups of batteries is measured every 1h, and an average value is taken and recorded until complete discharge. At the moment, the residual voltage of the waste battery is still 3.8 +/-0.1V after the waste battery is soaked for 24 hours.
Claims (10)
1. A discharge method of a waste lithium ion battery is characterized by comprising the following steps:
(1) disassembling the waste power battery pack into waste lithium ion battery monomers;
(2) measuring the pressure of the waste lithium ion battery monomer in the step (1), and separating the waste lithium ion battery monomer needing to be discharged to obtain the waste lithium ion battery monomer needing to be subjected to discharge treatment;
(3) putting a waste lithium ion battery monomer needing discharge treatment into a container filled with a salt solution, adding solid conductive powder into the container filled with the salt solution, and applying an external physical field to perform discharge operation to obtain a discharged waste lithium ion battery; the salt solution is CuSO4、FeSO4、ZnSO4、NiSO4、CoSO4One or more of the above, the salt solution has a concentration of 5% -50%, a temperature of 25-35 deg.C, and a pH of 7-10; the addition amount of the solid conductive powder is 1-10% of the mass of the salt solution.
2. The discharging method of the waste lithium ion battery according to claim 1, wherein the external physical field applied in the step (3) is one of an ultrasonic field, a flow field, and a coupling field of the ultrasonic field and the flow field; when the applied external physical field is one of an ultrasonic field and a coupling field of the ultrasonic field and the flow field, the ultrasonic field is applied through an ultrasonic generating device, and the rated power applied by the ultrasonic field is 30W-100W; when the applied external physical field is one of a flow field, an ultrasonic field and a coupling field of the flow field, the flow field is applied in a mechanical stirring mode, and the rotating speed of the mechanical stirring is 200-500 rpm.
3. The discharging method of the waste lithium ion battery according to claim 1, wherein the concentration of the salt solution in the step (3) is 5% -20%.
4. The discharging method of the waste lithium ion battery as claimed in claim 3, wherein the concentration of the salt solution in the step (3) is 10% -15%.
5. The method for discharging waste lithium ion batteries according to claim 1, wherein the pH of the salt solution in the step (3) is 7-8.
6. The method for discharging the waste lithium ion batteries according to claim 1, wherein the solid conductive powder in the step (3) is at least one of iron powder, zinc powder and copper powder.
7. The discharging method of the waste lithium ion batteries according to claim 1, wherein the addition amount of the solid conductive powder in the step (3) is 2-5% of the mass of the salt solution; and (4) the time that the voltage of the discharged waste lithium ion battery in the step (3) is lower than 1V is not higher than 12 h.
8. The discharging method of the waste lithium ion battery according to claim 1, wherein the waste lithium ion battery is one or more of a waste ternary power battery, a lithium cobaltate battery, a lithium manganate battery, a lithium nickelate battery and a lithium iron phosphate battery.
9. The discharging method of the waste lithium ion batteries according to claim 1, wherein the residual voltages of the waste power battery pack and the waste lithium ion battery in the step (1) are not lower than 1V.
10. The discharging method of the waste lithium ion batteries according to claim 9, wherein the residual voltage of the waste power battery pack and the waste lithium ion battery monomer in the step (1) is 3.8V to 3.85V.
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