CN117438682B - Method for completely discharging waste lithium ion battery - Google Patents
Method for completely discharging waste lithium ion battery Download PDFInfo
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- CN117438682B CN117438682B CN202311765093.2A CN202311765093A CN117438682B CN 117438682 B CN117438682 B CN 117438682B CN 202311765093 A CN202311765093 A CN 202311765093A CN 117438682 B CN117438682 B CN 117438682B
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- lithium ion
- discharge vessel
- discharge
- waste lithium
- ionic liquid
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 132
- 239000002699 waste material Substances 0.000 title claims abstract description 108
- 238000007599 discharging Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002608 ionic liquid Substances 0.000 claims abstract description 107
- 239000002245 particle Substances 0.000 claims abstract description 93
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 12
- -1 1-ethyl-3-methylimidazole tetrafluoroborate Chemical compound 0.000 claims description 10
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- RSUVDYIIMBESLX-UHFFFAOYSA-N C(CCC)N1CN(C=C1)C.B(O)(O)F.B(O)(O)F.B(O)(O)F.B(O)(O)F.B(O)(O)F.B(O)(O)F Chemical compound C(CCC)N1CN(C=C1)C.B(O)(O)F.B(O)(O)F.B(O)(O)F.B(O)(O)F.B(O)(O)F.B(O)(O)F RSUVDYIIMBESLX-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- WLWHLUQQCLCFNE-UHFFFAOYSA-N 1-ethenyl-3-methyl-2h-imidazole Chemical compound CN1CN(C=C)C=C1 WLWHLUQQCLCFNE-UHFFFAOYSA-N 0.000 claims description 3
- 230000004087 circulation Effects 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 9
- 239000002912 waste gas Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000428 dust Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003836 peripheral circulation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/441—Methods for charging or discharging for several batteries or cells simultaneously or sequentially
-
- 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
Abstract
The invention discloses a method for completely discharging a waste lithium ion battery, which relates to the technical field of battery recovery and comprises the following steps: arranging a plurality of waste lithium ion batteries on a plurality of discharge frames at intervals; arranging a plurality of discharge frames in a discharge vessel at intervals, and throwing conductive particles into the discharge vessel until the conductive particles cover a plurality of waste lithium ion batteries; adding ionic liquid into the discharge vessel until the ionic liquid submerges the conductive particles, and sealing the discharge vessel; pressurizing the sealed discharge vessel to a preset pressure, and intermittently vibrating the pressurized discharge vessel; and after waiting for the preset time, releasing the pressure of the discharge vessel, taking out the discharge frame, and discharging the waste lithium ion battery to obtain the discharge lithium battery. The invention combines conductive particles and ionic liquid to carry out pressurized discharge, has high discharge efficiency, can not corrode and pollute batteries, can not generate waste gas and dangerous waste liquid, and can be used repeatedly, thereby avoiding environmental pollution.
Description
Technical Field
The invention relates to the technical field of battery recovery, in particular to a method for completely discharging a waste lithium ion battery.
Background
With the continuous development of modern technology, lithium ion batteries have become the main energy supply source for many electronic products, new energy automobiles and energy storage systems. However, with the widespread use of lithium ion batteries, the problems of management and disposal of waste lithium ion batteries are becoming prominent. The waste lithium ion battery contains harmful substances such as lithium, cobalt, nickel, organic electrolyte and the like. Harmful substances in the waste lithium ion batteries can enter soil and underground water due to improper treatment, and the problem of environmental pollution is caused. In addition, the waste lithium ion battery can burn under improper conditions, release harmful gases and pose a threat to the atmospheric environment. How to recycle waste lithium ion batteries has become an urgent environmental and social challenge. Effectively managing and treating the waste lithium ion batteries has important significance for reducing environmental pollution, improving resource utilization efficiency and guaranteeing sustainable development.
At present, the recovery technology of waste lithium ion batteries tends to be mature, wherein crushing and sorting are necessary processes; however, the waste lithium ion battery still contains a small amount of electric energy, and electric spark is easy to generate during crushing and sorting and fire disaster is easy to be caused by high temperature, so that the method of completely discharging the waste lithium ion battery is extremely important in recycling the waste lithium ion battery. Currently, the discharging method of the waste lithium ion battery mainly comprises salt water discharging and conductive powder discharging. The brine discharge, namely, the waste lithium ion battery is soaked in the brine, the electric energy in the battery is consumed through the electrolysis of the brine, the discharge process is relatively mild, the treatment cost is low, but waste gas and dangerous waste liquid (containing electrolyte) such as hydrogen, oxygen, chlorine and the like are easy to generate, the battery shell and the internal pole piece are also easy to corrode and pollute, and the treatment speed is low (the common discharge period is 3-5 days). The conductive powder discharges, namely, the conductive carbon powder or the graphite powder is used as a conductive medium for discharging, and the conductive powder has the advantages of being suitable for most battery types, generating no three wastes in the discharging process, being simple to operate, but being poor in contact among the conductive powder, large in contact resistance and slow in discharging, and being easy to raise dust and pollute the environment in the feeding and discharging processes.
Therefore, the existing discharge method of the waste lithium ion battery is still to be further improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for completely discharging a waste lithium ion battery.
The invention provides a method for completely discharging a waste lithium ion battery, which comprises the following steps:
s1, arranging a plurality of waste lithium ion batteries on a plurality of discharge frames at intervals, and exposing the positive electrodes and the negative electrodes of the plurality of waste lithium ion batteries;
s2, arranging the discharge frames in a discharge vessel at intervals, and throwing conductive particles into the discharge vessel until the conductive particles cover the waste lithium ion batteries;
s3, adding ionic liquid into the discharge vessel until the ionic liquid submerges the conductive particles, and sealing the discharge vessel;
the ionic liquid comprises, by weight, 27-34 parts of 1-ethyl-3-methylimidazole tetrafluoroborate, 10-21 parts of 1-butyl-3-methylimidazole hexafluoroborate and 15-18 parts of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimine salt;
s4, pressurizing the sealed discharge vessel to a preset pressure, and intermittently vibrating the pressurized discharge vessel;
s5, after waiting for a preset time, discharging the pressure of the discharge vessel, taking out the discharge frames, and discharging the waste lithium ion batteries on the discharge frames to obtain a plurality of discharge lithium batteries.
Specifically, the particle size of the conductive particles is 1-10 mm, and the conductive particles are metal particles.
Specifically, in step S4, nitrogen is injected into the discharge vessel to pressurize, where the preset pressure ranges from 1000Pa to 100000Pa.
Specifically, in step S4, a plurality of vibration exciters are used to intermittently vibrate the discharge vessel, the vibration sub-range of the motor of each vibration exciter is 2500-3300 r/min, and the double-amplitude range of the vibration exciter is 2-4 mm;
vibrating the discharge vessel for 60-90 s every 30-40 min.
Specifically, after the discharge vessel is pressurized to a preset pressure, the ionic liquid in the discharge vessel circularly flows from bottom to top based on an external circulation pipeline, and the vertical flow velocity range of the ionic liquid is 0.2-0.5 m/s.
Specifically, the temperature of the ionic liquid is controlled to be 45-50 ℃.
Specifically, in step S5, the preset time ranges from 2 to 4 hours.
Specifically, in step S5, after waiting for a preset time, the ionic liquid in the discharge vessel is discharged from the bottom of the discharge vessel under pressure until the pressure in the discharge vessel is zero, and the discharged ionic liquid is filtered and decontaminated.
Specifically, after the pressure in the discharge vessel is zeroed, hot air is introduced from the top of the discharge vessel and gas is discharged from the bottom of the discharge vessel for 40 to 60 minutes.
Specifically, the ionic liquid also comprises 7-9 parts by weight of 1-vinyl-3-methylimidazole bistrifluoromethane sulfonyl imide salt.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the plurality of waste lithium ion batteries are arranged on the plurality of discharge frames at intervals, and then the plurality of discharge frames are arranged in the discharge vessel at intervals, so that the waste lithium ion batteries are prevented from being too concentrated, the waste lithium ion batteries are beneficial to fully contacting conductive particles and ionic liquid, the heat dissipation of the waste lithium ion batteries during discharging is also beneficial, and the waste lithium ion batteries are prevented from sinking to the bottom under the action of gravity;
the ionic liquid selected by the invention has the advantages of non-volatility, incombustibility, high heat resistance, strong electric conductivity, large heat capacity, stable property and the like, and the waste lithium ion battery is pressurized and discharged by combining the conductive particles and the ionic liquid, the gaps among the conductive particles are filled by utilizing the good electric conductivity and the fluid characteristics of the ionic liquid, and then the pressure is applied, so that the waste lithium ion battery can be more fully contacted with a discharge medium, and the discharge efficiency is effectively improved; the characteristic of large heat capacity of the ionic liquid is utilized, so that the heat generated by the discharge of the waste lithium ion battery can be effectively absorbed, the ionic liquid is non-volatile, nonflammable and high in heat resistance, and the safety of the discharge process of the waste lithium ion battery can be further ensured;
the ionic liquid selected by the invention does not corrode and pollute batteries, conductive particles, a discharge rack, a discharge vessel and the like, and components with specific proportions of the ionic liquid can enable the ionic liquid to withstand battery voltage of more than 4V, electrolysis does not occur, and the ionic liquid is used together with the conductive particles, so that on one hand, controllable conductivity can be realized, the waste lithium ion batteries can be stably discharged, and the phenomenon of thermal runaway caused by too fast discharge can be avoided; on the other hand, the generation of waste gases such as hydrogen, oxygen, chlorine and the like can be avoided, and the generation of dangerous waste liquid caused by the damage of the battery shell due to dissolution can also be avoided; in addition, the ionic liquid is not volatilized, conductive particles are not raised dust, and the pollution to the environment is small; the liquid ionic liquid and the granular conductive particles are more easily separated from the waste lithium ion battery, are convenient to recycle, can be repeatedly used, and are environment-friendly;
in addition, the intermittent vibration discharge vessel can fully fill and cover gaps among a plurality of waste lithium ion batteries with conductive particles and ionic liquid, avoid bubbles, and fully contact the conductive particles, the ionic liquid and the waste lithium ion batteries, thereby being beneficial to improving discharge efficiency.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for fully discharging a waste lithium ion battery in an embodiment of the invention;
fig. 2 is a voltage change schematic diagram of the discharging process of example 2;
fig. 3 is a voltage change schematic of the discharging process of comparative example 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Fig. 1 shows a flowchart of a method for completely discharging a waste lithium ion battery in an embodiment of the invention, including the following steps:
s1, arranging a plurality of waste lithium ion batteries on a plurality of discharge frames at intervals, and exposing the positive electrodes and the negative electrodes of the plurality of waste lithium ion batteries;
the waste lithium ion batteries are arranged on the discharge frames at intervals, so that the waste lithium ion batteries can be prevented from being too concentrated, the anode and the cathode of the waste lithium ion batteries are fully exposed, the waste lithium ion batteries, conductive particles and ionic liquid are fully contacted and discharged, heat dissipation is also facilitated when the waste lithium ion batteries are discharged, the waste lithium ion batteries can be prevented from sinking to the bottom under the action of gravity, the waste lithium ion batteries can not be disturbed by subsequent intermittent vibration, and the waste lithium ion batteries can be taken out conveniently after the discharge of the waste lithium ion batteries is completed.
Specifically, the discharge rack is made of aluminum alloy, and has light weight, high strength and good thermal conductivity; preferably, the discharge rack is made of high-strength aluminum alloy, and has long service life.
S2, arranging the discharge frames in a discharge vessel at intervals, and throwing conductive particles into the discharge vessel until the conductive particles cover the waste lithium ion batteries;
the plurality of discharge frames are arranged in the discharge vessel at intervals, so that the waste lithium ion batteries can be prevented from being too concentrated, the waste lithium ion batteries, conductive particles and ionic liquid can be fully contacted and discharged, and heat dissipation during discharging of the waste lithium ion batteries is also facilitated.
Specifically, the particle size of the conductive particles is 1-10 mm, and the conductive particles with proper particle size can be matched according to the size of the waste lithium ion battery, so that the waste lithium ion battery and the conductive particles can be fully contacted; if the particle size of the conductive particles is smaller than 1mm, dust is easy to generate, the conductive particles are easy to adhere to waste lithium ion batteries, recycling is difficult, and the ionic liquid is difficult to fully fill gaps among the conductive particles; if the particle size of the conductive particles is larger than 10mm, gaps among the conductive particles are too large, the contact with the waste lithium ion battery is poor, the contact resistance is large, and the discharge is slow.
Further, the conductive particles are metal particles, have good conductivity, and are firm and durable. Preferably, the metal particles are alloy particles, and the alloy particles consist of 60% -70% of copper, 20% -30% of zinc, 5% -10% of aluminum, 1% -5% of titanium and 1% -3% of zirconium, and have the advantages of good electrical conductivity and thermal conductivity, high strength, corrosion resistance and long-term repeated recycling.
S3, adding ionic liquid into the discharge vessel until the ionic liquid submerges the conductive particles, and sealing the discharge vessel;
the ionic liquid comprises, by weight, 27-34 parts of 1-ethyl-3-methylimidazole tetrafluoroborate, 10-21 parts of 1-butyl-3-methylimidazole hexafluoroborate and 15-18 parts of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimine salt, and the 1-ethyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hexafluoroborate and 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimine salt can keep a liquid state at a temperature above 12 ℃, and the three materials can be fully mutually dissolved, have good fluidity and have strong conductivity.
The ionic liquid selected by the invention has the advantages of non-volatility, incombustibility, high heat resistance, strong electric conductivity, large heat capacity, stable property and the like, and the waste lithium ion battery is discharged by combining the conductive particles and the ionic liquid, and gaps among the conductive particles are filled by utilizing good electric conductivity and fluid characteristics of the ionic liquid, so that the waste lithium ion battery can be more fully contacted with a discharge medium (namely the conductive particles and the ionic liquid), thereby effectively improving the discharge efficiency; the characteristic of large heat capacity of the ionic liquid is utilized, so that the heat generated by the discharge of the waste lithium ion battery can be effectively absorbed, and the ionic liquid is non-volatile, nonflammable and high in heat resistance, so that the safety of the discharge process of the waste lithium ion battery can be further ensured.
The ionic liquid selected by the invention does not corrode and pollute batteries, conductive particles, a discharge rack, a discharge vessel and the like, and components with specific proportions of the ionic liquid can enable the ionic liquid to withstand battery voltage of more than 4V, electrolysis does not occur, and the ionic liquid is used together with the conductive particles, so that on one hand, controllable conductivity can be realized, the waste lithium ion batteries can be stably discharged, and the phenomenon of thermal runaway caused by too fast discharge can be avoided; on the other hand, the generation of waste gases such as hydrogen, oxygen, chlorine and the like can be avoided, and the generation of dangerous waste liquid caused by the damage of the battery shell due to dissolution can also be avoided; in addition, the ionic liquid is not volatilized, conductive particles are not raised dust, and the pollution to the environment is small; the liquid ionic liquid and the granular conductive particles are easier to separate from the waste lithium ion battery, are convenient to recycle, can be repeatedly used, and are environment-friendly.
In some specific embodiments, the ionic liquid further comprises 7-9 parts by weight of 1-vinyl-3-methylimidazole bis (trifluoromethanesulfonyl imide) salt, wherein the 1-vinyl-3-methylimidazole bis (trifluoromethanesulfonyl imide) salt can be polymerized rapidly at high temperature, the temperature rising speed is slowed down, and the safety of the discharge process of the waste lithium ion battery can be improved.
S4, pressurizing the sealed discharge vessel to a preset pressure, and intermittently vibrating the pressurized discharge vessel;
the discharge vessel is pressurized, so that the ionic liquid can fully fill gaps among the conductive particles, the conductive particles can be more compact, and the waste lithium ion batteries can be more fully contacted with a discharge medium; the intermittent vibration discharge vessel can further enable the conductive particles and the ionic liquid to fully fill and cover gaps among a plurality of waste lithium ion batteries, avoid bubbles, and enable the conductive particles, the ionic liquid and the waste lithium ion batteries to fully contact, thereby being beneficial to improving discharge efficiency.
In some specific embodiments, nitrogen is injected into the discharge vessel for pressurization, and the preset pressure ranges from 1000Pa to 100000Pa; nitrogen is insoluble in 1-ethyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hexafluoroborate and 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyliminamide salts, so that the discharge vessel can be pressurized; the preset pressure of 1000-100000 Pa is enough to enable the ionic liquid to fully fill gaps among the conductive particles and also is enough to enable the conductive particles to be more compact; under the pressure condition of 1000-100000 Pa, the ionic liquid can keep good fluidity, and can also show good adhesion to conductive particles and waste lithium ion batteries, thereby being beneficial to the waste lithium ion batteries to be fully contacted with a discharge medium, and further being beneficial to improving the discharge efficiency of the waste lithium ion batteries.
In some specific embodiments, a plurality of vibration exciters are used for intermittently vibrating the discharge vessel, the vibration frequency range of a motor of each vibration exciter is 2500-3300 r/min, the double-amplitude range of each vibration exciter is 2-4 mm, and the discharge vessel is vibrated for 60-90 s every 30-40 min, so that the discharge vessel and conductive particles, ionic liquid, waste lithium ion batteries and the like in the discharge vessel can be fully vibrated, on one hand, the conductive particles, the ionic liquid and the waste lithium ion batteries are fully contacted, and the discharge efficiency is improved; on the other hand, the conductive particles can be prevented from being adhered together due to the discharge of the waste lithium ion battery.
Specifically, the total exciting force of the plurality of vibration exciters is A, the total weight of the plurality of vibration exciters, the discharge vessel, the discharge rack, the plurality of waste lithium ion batteries, the conductive particles and the ionic liquid is B, and the constraint relation of A and B is as follows: a is more than 47 percent Bg, g is gravity acceleration; thus, the conductive particles can be fully vibrated, and overload work of the vibration exciter can be avoided; moreover, the vibration energy accelerates the movement of the ionic liquid, thereby improving the discharge rate. In addition, the ionic liquid has lubricating effect on the conductive particles, so that the conductive particles have little abrasion in vibration and can be reused for a long time.
In some embodiments, after pressurizing the discharge vessel to a preset pressure, circulating the ionic liquid in the discharge vessel from bottom to top based on a peripheral circulation line, wherein the ionic liquid has a vertical flow rate ranging from 0.2 to 0.5m/s. The ionic liquid flows in the discharge vessel, so that heat generated during discharge of the waste lithium ion battery can be taken away, and heat in-situ accumulation is avoided; the ionic liquid can circularly flow from bottom to top, so that the ionic liquid can be ensured to be filled in gaps among the conductive particles at any time, and the flowing fault of the ionic liquid is avoided; the proper vertical flow speed can promote the migration of anions and cations and improve the discharge efficiency.
Specifically, the temperature of the ionic liquid is controlled to be 45-50 ℃, under the temperature condition, the discharge speed of the waste lithium ion battery can be effectively improved, and meanwhile, the safety can be ensured.
S5, after waiting for a preset time, discharging the pressure of the discharge vessel, taking out the discharge frames, and discharging the waste lithium ion batteries on the discharge frames to obtain a plurality of discharge lithium batteries.
Specifically, the preset time is within a range of 2-4 hours, which is enough for completely discharging the waste lithium ion battery; furthermore, the temperature of the ionic liquid in the external circulation pipeline can be monitored, and when the temperature of the ionic liquid flowing out of the discharge vessel is more than 50 ℃, the waste lithium ion battery is still discharged; when the temperature of the ionic liquid flowing out of the discharge vessel is monitored to be between 45 and 50 ℃ and is maintained for more than 15 minutes, the temperature of the ionic liquid is reduced to between 15 and 20 ℃; and when the temperature of the ionic liquid flowing out of the discharge vessel is monitored to be 15-20 ℃ and is maintained for more than 15min, the discharge of the waste lithium ion battery is completed.
In some embodiments, after waiting for a preset time, discharging the ionic liquid in the discharge vessel from the bottom of the discharge vessel under pressure until the pressure in the discharge vessel is zero, filtering the discharged ionic liquid to remove impurities, and recycling. The bottom of the discharge vessel is provided with the liquid outlet with the filter screen, the ionic liquid is discharged from the bottom of the discharge vessel by using pressure, the discharge speed is high, the operation is simple, the ionic liquid is discharged cleanly, and the residue is less.
Further, after the pressure in the discharge vessel is reset to zero, hot air is introduced from the top of the discharge vessel, and gas is discharged from the bottom of the discharge vessel for 40-60 min, so that the ionic liquid remained on the surfaces of the conductive particles and the waste lithium ion batteries can be blown away, and the ionic liquid is prevented from adhering to the conductive particles and the waste lithium ion batteries.
Specifically, the temperature range of the hot air is 60-65 ℃, and the flow speed range of the hot air is 10-20 m/s, so that residual ionic liquid can be ensured to be blown away.
In some specific embodiments, after the pressure in the discharge vessel is reset, the conductive particles and the waste lithium ion batteries in the discharge vessel are sprayed with hot water for 15-30 min, and the ionic liquid remained on the surfaces of the conductive particles and the waste lithium ion batteries can be washed away, so that the ionic liquid is prevented from adhering to the conductive particles and the waste lithium ion batteries.
Specifically, the temperature range of the hot water is 50-55 ℃, and the flow range of the hot water is 16-20L/s, so that the residual ionic liquid can be guaranteed to be washed away.
In some embodiments, after the pressure in the discharge vessel has been zeroed, the vessel is sprayed with hot water for 15 minutes and then dried with hot air for 40 minutes.
In some embodiments, the discharge vessel is grounded, reducing charge accumulation to improve the safety of the discharge process.
Example 1
(1) Arranging 100 single 18650 lithium ion batteries (the voltage of a single battery is more than 4V) on two discharge frames at intervals, and exposing the positive and negative poles of all 18650 lithium ion batteries;
(2) Two discharge racks are arranged in a discharge vessel (volume 15L) at intervals, and alloy particles with the particle size of 1mm are put into the discharge vessel until the alloy particles cover all 18650 lithium ion batteries;
(3) Adding ionic liquid into the discharge vessel until the ionic liquid submerges all alloy particles, and sealing the discharge vessel;
the ionic liquid comprises, by weight, 30 parts of 1-ethyl-3-methylimidazole tetrafluoroborate, 16 parts of 1-butyl-3-methylimidazole hexafluoroborate and 16 parts of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimine salt;
(4) Pressurizing the sealed discharge vessel to 100kPa and intermittently vibrating the pressurized discharge vessel; intermittently vibrating the discharge vessel by using a vibration exciter, wherein the vibration sub-range of a motor of the vibration exciter is 2500r/min, and the double-amplitude range of the vibration exciter is 2mm; vibrating the discharge vessel for 60s every 30 min;
after pressurizing the discharge vessel to 100kPa, circulating the ionic liquid in the discharge vessel from bottom to top based on an external circulating pipeline, wherein the vertical flow rate range of the ionic liquid is 0.2m/s; controlling the temperature of the ionic liquid at 45 ℃;
(5) After waiting for 2 hours, releasing the pressure of the discharge vessel, taking out the two discharge frames, and discharging the waste lithium ion batteries on the two discharge frames to obtain 100 discharge lithium batteries;
(6) The voltage of 100 discharged lithium batteries was measured and the results are shown in table 1:
comparative example 1
(1) Arranging 100 single 18650 lithium ion batteries (the voltage of a single battery is more than 4V) on two discharge frames at intervals, and exposing the positive and negative poles of all 18650 lithium ion batteries;
(2) Two discharge racks are arranged in a discharge vessel (volume 15L) at intervals, alloy particles with the particle size of 1mm are put into the discharge vessel until the alloy particles cover all 18650 lithium ion batteries, and then the discharge vessel is sealed;
(3) Pressurizing the sealed discharge vessel to 100kPa and intermittently vibrating the pressurized discharge vessel; intermittently vibrating the discharge vessel by using a vibration exciter, wherein the vibration sub-range of a motor of the vibration exciter is 2500r/min, and the double-amplitude range of the vibration exciter is 2mm; vibrating the discharge vessel for 60s every 30 min;
(4) After waiting for 2 hours, releasing the pressure of the discharge vessel, taking out the two discharge frames, and discharging the waste lithium ion batteries on the two discharge frames to obtain 100 discharge lithium batteries;
(5) The voltage of 100 discharged lithium batteries was measured and the results are shown in table 2:
from example 1 and comparative example 1, the discharge efficiency of the lithium ion battery is significantly higher when the ionic liquid is added to the discharge vessel; in the embodiment 1, the ionic liquid participates in the discharge of the lithium ion battery, and after 100 single 18650 lithium ion batteries are discharged for 2 hours, the voltage values are all reduced to below 2V, and the discharge is completed; in comparative example 1, no ionic liquid was involved in the discharge of lithium ion batteries, and after 100 single 18650 lithium ion batteries were discharged for 2 hours, the voltage of 40 lithium ion batteries was not less than 2V, and the discharge was not completed.
Example 2
(1) 10 single 18650 lithium ion batteries (single battery voltage is 4V) are arranged on a discharge rack at intervals, and the positive and negative poles of all 18650 lithium ion batteries are exposed;
(2) A discharge frame is arranged in a discharge vessel (volume 5L), and alloy particles with the particle size of 10mm are put into the discharge vessel until the alloy particles cover all 18650 lithium ion batteries;
(3) Adding ionic liquid into the discharge vessel until the ionic liquid submerges all alloy particles, and sealing the discharge vessel;
the ionic liquid comprises, by weight, 30 parts of 1-ethyl-3-methylimidazole tetrafluoroborate, 16 parts of 1-butyl-3-methylimidazole hexafluoroborate and 16 parts of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimine salt;
(4) Pressurizing the sealed discharge vessel to 1000Pa, and intermittently vibrating the pressurized discharge vessel; a vibration exciter is used for intermittently vibrating the discharge vessel, the vibration sub-range of a motor of the vibration exciter is 3000r/min, and the double-amplitude range of the vibration exciter is 3mm; vibrating the discharge vessel for 60s every 40 min;
pressurizing the discharge vessel to 1000Pa, and circulating the ionic liquid in the discharge vessel from bottom to top based on an external circulating pipeline, wherein the vertical flow rate range of the ionic liquid is 0.3m/s; controlling the temperature of the ionic liquid at 50 ℃;
(5) Releasing pressure every 30min, taking out the discharge frame, measuring the voltage values of 10 single 18650 lithium ion batteries on the discharge frame, immediately embedding the voltage values into alloy particles after the measurement is finished, keeping the ion liquid immersed in all the alloy particles, and continuing the pressurizing discharge (each operation must be completed within 5min, so as to reduce the influence on the discharge effect as much as possible);
stopping measurement when the voltage values of the 10 monomer 18650 lithium ion batteries are smaller than 2V; example 2 was discharged for 4 hours altogether;
(6) The average value of each measurement result is taken to form a graph, as shown in fig. 2, and fig. 2 shows a voltage variation schematic diagram of the discharging process of example 2.
Comparative example 2
(1) 10 single 18650 lithium ion batteries (single battery voltage is 4V) are arranged on a discharge rack at intervals, and the positive and negative poles of all 18650 lithium ion batteries are exposed;
(2) A discharge frame is arranged in a discharge vessel (volume 5L), and alloy particles with the particle size of 10mm are put into the discharge vessel until the alloy particles cover all 18650 lithium ion batteries;
(3) Adding an ionic liquid into the discharge vessel until the ionic liquid submerges all alloy particles, wherein the discharge vessel is not sealed;
the ionic liquid comprises, by weight, 30 parts of 1-ethyl-3-methylimidazole tetrafluoroborate, 16 parts of 1-butyl-3-methylimidazole hexafluoroborate and 16 parts of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimine salt;
(4) Intermittently vibrating the discharge vessel; a vibration exciter is used for intermittently vibrating the discharge vessel, the vibration sub-range of a motor of the vibration exciter is 3000r/min, and the double-amplitude range of the vibration exciter is 3mm; vibrating the discharge vessel for 60s every 40 min;
circulating the ionic liquid in the discharge vessel from bottom to top based on the peripheral circulation pipeline, wherein the vertical flow velocity range of the ionic liquid is 0.3m/s; controlling the temperature of the ionic liquid at 50 ℃;
(5) Taking out the discharge rack every 60min, measuring the voltage values of 10 single 18650 lithium ion batteries on the discharge rack, immediately embedding the 10 single 18650 lithium ion batteries into the alloy particles after the measurement is finished, and keeping all the alloy particles immersed by the ionic liquid for continuous discharge (each operation must be completed within 5min, so as to minimize the influence on the discharge effect);
stopping measurement when the voltage values of the 10 monomer 18650 lithium ion batteries are smaller than 2V; comparative example 2 was discharged for 24 hours altogether;
(6) The average value of each measurement result was taken to make a graph as shown in fig. 3, and fig. 3 shows a voltage change schematic of the discharge process of comparative example 2.
From the results of example 2 and comparative example 2, the pressurization has a very significant effect on the discharge efficiency of the lithium ion battery, and the pressurization can significantly improve the discharge efficiency of the lithium ion battery; in example 2, the sealed discharge vessel was pressurized to 1000pa, and 10 single 18650 lithium ion batteries were discharged for 4 hours, and the voltage value was reduced to 2V or less; in comparative example 2, the discharge vessel was not pressurized and 10 single 18650 lithium ion batteries took 24 hours to complete the discharge.
The above description is made in detail of a method for completely discharging a waste lithium ion battery provided by the embodiment of the present invention, and specific examples should be adopted herein to illustrate the principles and embodiments of the present invention, where the above description of the examples is only for helping to understand the method and core ideas of the present invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (8)
1. The method for completely discharging the waste lithium ion battery is characterized by comprising the following steps of:
s1, arranging a plurality of waste lithium ion batteries on a plurality of discharge frames at intervals, and exposing the positive electrodes and the negative electrodes of the plurality of waste lithium ion batteries;
s2, arranging the discharge frames in a discharge vessel at intervals, and throwing conductive particles into the discharge vessel until the conductive particles cover the waste lithium ion batteries;
the conductive particles are alloy particles, and the alloy particles consist of 60% -70% of copper, 20% -30% of zinc, 5% -10% of aluminum, 1% -5% of titanium and 1% -3% of zirconium;
s3, adding ionic liquid into the discharge vessel until the ionic liquid submerges the conductive particles, and sealing the discharge vessel;
the ionic liquid comprises, by weight, 27-34 parts of 1-ethyl-3-methylimidazole tetrafluoroborate, 10-21 parts of 1-butyl-3-methylimidazole hexafluoroborate, 15-18 parts of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimine salt and 7-9 parts of 1-vinyl-3-methylimidazole bistrifluoromethylsulfonylimine salt;
s4, pressurizing the sealed discharge vessel to a preset pressure, and intermittently vibrating the pressurized discharge vessel;
injecting nitrogen into the discharge vessel for pressurization, wherein the preset pressure is 1000-100000 Pa;
s5, after waiting for a preset time, discharging the pressure of the discharge vessel, taking out the discharge frames, and discharging the waste lithium ion batteries on the discharge frames to obtain a plurality of discharge lithium batteries.
2. The method for completely discharging the waste lithium ion battery according to claim 1, wherein the particle size of the conductive particles is 1-10 mm.
3. The method for completely discharging the waste lithium ion battery according to claim 1, wherein in the step S4, a plurality of vibration exciters are used for intermittently vibrating the discharge vessel, the vibration frequency range of a motor of each vibration exciter is 2500-3300 r/min, and the double-amplitude range of the vibration exciter is 2-4 mm;
vibrating the discharge vessel for 60-90 s every 30-40 min.
4. The method for completely discharging the waste lithium ion battery according to claim 1, wherein after the discharge vessel is pressurized to a preset pressure, the ionic liquid in the discharge vessel is circulated from bottom to top based on an external circulation pipeline, and the vertical flow rate of the ionic liquid ranges from 0.2m/s to 0.5m/s.
5. The method for completely discharging the waste lithium ion battery according to claim 1, wherein the temperature of the ionic liquid is controlled to be 45-50 ℃.
6. The method for completely discharging a waste lithium ion battery according to claim 1, wherein in the step S5, the preset time is in the range of 2 to 4 hours.
7. The method for completely discharging the waste lithium ion battery according to claim 1, wherein in the step S5, after waiting for a preset time, the ionic liquid in the discharge vessel is discharged from the bottom of the discharge vessel under pressure until the pressure in the discharge vessel is zero, and the discharged ionic liquid is subjected to filtration and impurity removal treatment.
8. The method of completely discharging a waste lithium ion battery according to claim 1, wherein after the pressure in the discharge vessel is zeroed, hot air is introduced from the top of the discharge vessel and gas is discharged from the bottom of the discharge vessel for 40 to 60 minutes.
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| CN116742174A (en) * | 2023-04-19 | 2023-09-12 | 江苏理工学院 | Method for separating positive electrode active material of waste lithium battery from aluminum foil |
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