CN110391474B - Discharging method of waste lithium ion battery - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 65
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 238000007599 discharging Methods 0.000 title claims abstract description 50
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 62
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 14
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004020 conductor Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 229920000767 polyaniline Polymers 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 150000004763 sulfides Chemical class 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 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims 1
- 239000012266 salt solution Substances 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 8
- 238000011160 research Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 76
- 239000010926 waste battery Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 21
- 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
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent 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
- 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
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 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
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 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
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the field of waste lithium ion battery recovery, and particularly discloses a high-efficiency clean discharging method for waste lithium ion batteries, which comprises the steps of placing a battery pack of the waste lithium ion battery or a battery monomer obtained after disassembly into a solution (salt solution) dissolved with reducing salt for discharging; the reducing salt discharges preferentially to OH-in aqueous solution. The reducing salt is water-soluble sulfide salt and/or hydrosulfide salt. According to research, the invention discovers that the residual electric quantity of the waste lithium ion battery is discharged in the salt solution by an oxidation-reduction method. The method can realize high-efficiency discharge, obviously shortens the discharge time, is beneficial to achieving thorough discharge (discharge to 0V), and has obvious advantages compared with the discharge method which can only achieve 0.7V in the prior art.
Description
Technical Field
The invention relates to the field of waste lithium ion battery recovery, in particular to efficient clean discharge of a waste lithium ion battery, and belongs to the field of waste lithium ion battery recovery.
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 a discharge operation must be performed to ensure safety of personnel and equipment to leave the voltageThe voltage is brought within a safe range. 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 5-10% NaCl solution is generally adopted for discharge operation. 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 battery discharge operation is carried out by adopting 5-10% NaCl salt solution, so that the residual voltage of the waste battery can meet the requirement of safe disassembly, but the discharge rate is slow, the residual voltage is reduced to below 1V by soaking for more than 24h, and chloride ions which are difficult to remove are introduced into the leachate to influence 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, the discharge time is long (generally, more than 24 hours), the discharge effect is not ideal, the discharge can only be about 0.7V, and the battery pack is easily corroded in the treatment process, so that the highly toxic electrolyte is leaked 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 and clean discharge method for the lithium ion battery, and aims to improve the discharge effect while shortening the discharge time.
A discharge method of waste lithium ion batteries is characterized in that battery packs of the waste lithium ion batteries or battery monomers obtained by disassembly are placed in a solution (also called a salt solution) dissolved with reducing salt for discharging;
the reducing salt discharges preferentially to OH-in aqueous solution.
According to research, the invention discovers that the residual electric quantity of the waste lithium ion battery is discharged in the salt solution by an oxidation-reduction method. The method can realize high-efficiency discharge, and researches show that the method not only obviously shortens the discharge time, but also is beneficial to achieving complete 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.
According to the technical scheme of the invention, the reducibility in aqueous solution is necessary to be prior to OH-. Preferably, the reducing salt is a water-soluble sulfide salt and/or hydrosulfide salt.
More preferably, the water-soluble sulfide salt is an alkali metal sulfide; the hydrosulfide salt is alkali metal hydrosulfide.
More preferably, the reducing salt is at least one of sodium sulfide, potassium sulfide, sodium hydrosulfide and potassium hydrosulfide.
Most preferably, the reducing salt is sodium sulfide. Researches show that the solution of the sodium sulfide is adopted to carry out discharge, the effect is better, the discharge time is shorter, the discharge effect (discharge degree) can easily reach 0V, and the solution has better discharge effect.
The solution dissolved with the reducing salt is preferably an aqueous solution of the reducing salt, the solution system is allowed to contain some solvents except water, and the solvent is preferably a solvent which is infinitely miscible with water.
Research also finds that controlling the mass percentage of the reducing salt in a proper solution is helpful for further improving the discharge efficiency and further improving the discharge effect.
Preferably, the concentration of the reducing salt in the solution in which the reducing salt is dissolved is not less than 5 wt%. At this preferred concentration, the discharge can be made to 0V at 14h, and the technical effect is excellent.
More preferably, the concentration of the reducing salt in the solution in which the reducing salt is dissolved is 5 to 20 wt%.
More preferably, the concentration of the reducing salt in the solution containing the reducing salt dissolved therein is 10 to 15 wt%. Research shows that under the preferable concentration, the time from discharging to 0V can be shortened to 6h, the discharging effect is better, and the discharging efficiency is better.
The inventor researches and discovers that the discharging effect can be further improved, the discharging time can be shortened, and the discharging effect can be improved by controlling the pH value in the discharging process, the temperature in the discharging process, adding a conductive material in the solution dissolved with the reducing salt and the like in the discharging process.
Preferably, the pH of the solution in which the reducing salt is dissolved is 7 to 10. The pH is the pH of the initial solution with the reducing salt dissolved; further preferably, the pH is 7 to 8.
Further preferably, the pH of the solution system in which the reducing salt is dissolved is 7 to 7.5.
Preferably, the temperature of the solution in which the reducing salt is dissolved is controlled to 25 to 35 ℃ during the discharging. The temperature of the solution dissolved with the reducing salt is also the temperature of the discharging process.
Further preferably, the temperature of the solution in which the reducing salt is dissolved is controlled to 25 to 30 ℃ during the discharging. The discharge efficiency can be further improved and the discharge effect can be further improved by controlling the discharge temperature to be the optimal discharge temperature.
Preferably, the solution in which the reducing salt is dissolved further contains a conductive material. By adding the conductive material into the solution dissolved with the reducing salt in the discharging process, the discharging effect can be further improved, and the discharging efficiency is improved.
Preferably, the conductive material is at least one of graphite, graphite oxide and conductive polyaniline.
Preferably, the volume fraction of the conductive material in the solution in which the reducing salt is dissolved is 5 to 20%.
Preferably, the waste lithium ion battery is one or more of a waste ternary power battery, a lithium cobaltate battery, a lithium manganate battery and a lithium iron phosphate battery.
Preferably, the residual voltage of the battery pack and the battery unit is not lower than 1V, and preferably 3.8V-3.85V.
Preferably, the time for which the voltage after discharge is lower than 1V is not higher than 14 h. The discharge time of the invention is obviously shorter than that of the existing method, and even so, the invention can ensure better discharge effect.
The invention discloses a preferable new high-efficiency clean discharging method of waste lithium ion batteries, which mainly comprises the following steps:
step 1: disassembling the waste power battery pack into waste lithium ion battery monomers;
step 2: carrying out pressure measurement operation on the waste lithium ion battery monomer obtained in the step 1, and quickly and continuously separating out the battery monomer needing to be discharged by using the conventional equipment to obtain the battery monomer needing to be discharged;
and step 3: putting the battery monomer which is obtained in the step 2 and needs to be subjected to discharge treatment into containers filled with different salt solutions for discharge operation, adjusting physical parameters of the solutions and adding solid conductive powder to enhance the discharge effect;
and 4, step 4: 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 waste power battery pack in the step 1 is preferably a waste ternary power battery pack.
The battery cell needing discharging in the step 2 is preferably a battery cell with residual voltage higher than 1V.
The salt solution in the step 3 is one or more of sodium sulfide and sodium hydrosulfide solution; the physical parameters of the solution refer to one or more of the temperature, the PH value and the concentration of the solution; the solid powder is one or more of graphite, graphite oxide and conductive polyaniline.
The concentration of the salt solution in the step 3 is 5-20%, the temperature is 25-35 ℃, and the PH value is about 7; the mass fraction of the added solid powder is 5-20%.
The invention aims to provide a novel discharge method for efficiently cleaning waste lithium ion batteries. The anode releases electrons and the cathode obtains electrons by utilizing a simple electrolysis principle, and the solution of reducing salt which is easy to discharge hydroxide radicals is used as a discharge medium to replace the currently mainstream adopted 5-10% NaCl solution, so that the introduction of chloride ions is avoided, and the high-efficiency clean discharge of the waste lithium ion battery can be realized.
Has the advantages 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 technology for realizing solid-liquid common discharge by mixing the sodium sulfide solution, the sodium sulfide solution and the conductive powder is provided for the first time, so that the use of a main discharge medium NaCl salt solution is avoided, no chloride ions are introduced, the generation of harmful gas chlorine is avoided, the subsequent production is not influenced, and the efficient continuous clean discharge of the waste lithium ion battery can be realized.
3) The solid-liquid synergistic discharge technology of the sodium sulfide solution or the sodium sulfide solution and the conductive powder is adopted to avoid damage to the battery shell in the discharge process of the waste battery, and the leakage of electrolyte and water quality pollution caused by corrosion of other discharge media such as sodium hydroxide and sodium chloride solution to the battery shell are avoided.
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 invention obviously shortens the discharge time, and the time for discharging to 0V can be shortened to 6 h.
Drawings
Fig. 1 is a graph of the effect of discharging a battery using sodium sulfide solutions of different concentrations.
Figure 2 is a graph of the discharge effect of batteries using sodium sulfite solutions of different concentrations.
Detailed description of the preferred embodiments
The following are exemplary embodiments of the invention, but it should be understood that the invention is not limited to these embodiments.
The following percentages, unless otherwise stated, are percentages by mass.
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 single batteries, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each single battery, separating the single batteries with the residual voltage higher than 1V, and entering a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in 5 percent of Na2And (3) in an open container of the S solution, adjusting the pH value of the solution to 7-7.5 at the temperature of 25 ℃, measuring the residual voltage of 5 groups of batteries every 1 hour and recording until the discharge is complete. At this time, the residual voltage of the waste battery after soaking for 14h is reduced to 0V.
Example 2
The method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into single batteries, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each single battery, separating the single batteries with the residual voltage higher than 1V, and entering 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% Na2S solution, the pH value of the solution is adjusted to 7-7.5, the temperature is 30 ℃, the residual voltage of the 5 groups of batteries is measured every 1 hour and recorded until the discharge is complete. At this time, the residual voltage of the waste battery is reduced to 0V after soaking for 12 h.
Example 3
The method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into single batteries, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each single battery, separating the single batteries with the residual voltage higher than 1V, and entering a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in 10 percent Na2And (3) in an open container of the S solution, adjusting the pH value of the solution to 7-7.5 at the temperature of 30 ℃, measuring the residual voltage of 5 groups of batteries every 1 hour and recording until the discharge is complete. At this time, the residual voltage of the waste battery is reduced to 0V after soaking for 6 hours.
Example 4
The method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into single batteries, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each single battery, separating the single batteries with the residual voltage higher than 1V, and entering a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in 10 percent Na2And (3) in an open container of the S solution, adjusting the pH value of the solution to 7-7.5, controlling the temperature to be 30 ℃, then adding 10 (volume)% of conductive polyaniline powder, stirring until the mixture is uniformly mixed, measuring the residual voltage of 5 groups of batteries every 1 hour, and recording until the discharge is complete. At this time, the residual voltage of the waste battery is reduced to 0V after soaking for 4.5 h. 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 Na2SO3Replacing said Na2S, specifically comprising the following steps:
the method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into single batteries, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each single battery, separating the single batteries with the residual voltage higher than 1V, and entering 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% Na2SO3 solution, the pH value of the solution is adjusted to 7-7.5, the temperature is 25 ℃, the residual voltage of the 5 groups of batteries is measured every 1 hour and recorded until the discharge is complete. At this time, the residual voltage of the waste battery after soaking for 24 hours is 1.4V.
Comparative example 2
This comparative example discusses the use of Na2SO3Replacing said Na2S, and discharging at 30 ℃, specifically as follows:
the method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into single batteries, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each single battery, separating the single batteries with the residual voltage higher than 1V, and entering 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% Na2SO3 solution, the pH value of the solution is adjusted to 7-7.5, the temperature is 30 ℃, the residual voltage of the 5 groups of batteries is measured every 1 hour and recorded until the discharge is complete. At this time, the residual voltage of the waste battery after soaking for 24 hours is 1.25V.
Comparative example 3
This comparative example discusses the use of Na2SO3Replacing said Na2S, and discharges at 10% concentration, as follows:
the method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into single batteries, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each single battery, separating the single batteries with the residual voltage higher than 1V, and entering a discharging process. 5 groups of battery monomers with residual voltage of 3.8V-3.85V are soaked in an open container filled with 10% Na2SO3 solution, the pH value of the solution is adjusted to 7-7.5, the temperature is 30 ℃, the residual voltage of 5 groups of batteries is measured every 1 hour and 7 is recorded until the discharge is complete. At this time, the residual voltage of the waste battery after soaking for 24 hours is 1.1V.
Comparative example 4
This comparative example discusses, using conventional NaCl discharge, as follows:
the method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into single batteries, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each single battery, separating the single batteries with the residual voltage higher than 1V, and entering 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 ℃, the residual voltage of the 5 groups of batteries is measured every 1 hour 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.
Comparative example 5
Blank control:
the method comprises the steps of adopting automatic disassembling equipment to disassemble a waste power battery pack into single batteries, then continuously adopting the existing waste battery residual voltage detection equipment to detect the residual voltage of each single battery, separating the single batteries with the residual voltage higher than 1V, and entering 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 ℃, the residual voltage of the 5 groups of batteries is measured every 1 hour and recorded until the discharge is complete. At this time, the residual voltage of the waste battery after being soaked for 24 hours is 3.8 +/-0.3V.
Claims (14)
1. A discharge method of waste lithium ion batteries is characterized in that battery packs of the waste lithium ion batteries or battery monomers obtained by disassembly are placed in a solution dissolved with reducing salt for discharge;
the reducing salt discharges preferentially to OH-in aqueous solution.
2. The method for discharging waste lithium ion batteries according to claim 1, wherein the reducing salt is a water-soluble sulfide salt and/or hydrosulfide salt.
3. The method for discharging the waste lithium ion batteries according to claim 2, wherein the reducing salt is at least one of sodium sulfide, potassium sulfide, sodium hydrosulfide and potassium hydrosulfide.
4. The discharge method of the waste lithium ion batteries according to any one of claims 1 to 3, wherein the concentration of the reducing salt in the solution in which the reducing salt is dissolved is not less than 5 wt%.
5. The discharging method of the waste lithium ion battery as claimed in claim 4, wherein the concentration of the reducing salt in the solution dissolved with the reducing salt is 5-20 wt%.
6. The method of discharging spent lithium ion batteries according to claim 1, wherein the pH of the solution in which the reducing salt is dissolved is 7 to 10.
7. The discharging method of waste lithium ion batteries according to claim 1, wherein the temperature of the solution dissolved with the reducing salt is controlled to be 25-35 ℃ during the discharging process.
8. The discharging method of waste lithium ion batteries according to claim 1, wherein the temperature of the solution dissolved with the reducing salt is controlled to be 25-30 ℃ during the discharging process.
9. The discharging method of waste lithium ion batteries according to claim 1, wherein the solution dissolved with the reducing salt further contains a conductive material, and the conductive material is at least one of graphite, graphite oxide, conductive polyaniline and polypyrrole.
10. The method for discharging spent lithium ion batteries according to claim 9, wherein the volume fraction of the conductive material in the solution in which the reducing salt is dissolved is 5 to 20%.
11. The discharging method of waste lithium ion batteries according to claim 1, wherein the waste lithium ion batteries are one or more of waste ternary power batteries, lithium cobaltate batteries, lithium manganate batteries and lithium iron phosphate batteries.
12. The method for discharging waste lithium ion batteries according to claim 11, wherein the residual voltage of the battery pack and the battery cells is not less than 1V.
13. The method for discharging waste lithium ion batteries according to claim 12, wherein the residual voltage of the battery pack and the battery cells is 3.8V to 3.85V.
14. The method for discharging the waste lithium ion batteries according to claim 1, wherein the time for the voltage to be lower than 1V after the discharge is not higher than 14 h.
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| CN113809426A (en) * | 2021-09-17 | 2021-12-17 | 格林美股份有限公司 | Discharging method of waste lithium ion battery |
| CN114094216A (en) * | 2021-10-29 | 2022-02-25 | 格林美股份有限公司 | Efficient discharge method for waste lithium ion battery module |
| CN116073003B (en) * | 2023-03-13 | 2023-07-14 | 广东金晟新能源股份有限公司 | Residual electric quantity discharging device for ternary lithium battery single cell |
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