CN117256065A - Treatment method for recycling waste batteries - Google Patents
Treatment method for recycling waste batteries Download PDFInfo
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- CN117256065A CN117256065A CN202280025696.6A CN202280025696A CN117256065A CN 117256065 A CN117256065 A CN 117256065A CN 202280025696 A CN202280025696 A CN 202280025696A CN 117256065 A CN117256065 A CN 117256065A
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- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000010926 waste battery Substances 0.000 title abstract description 15
- 238000004064 recycling Methods 0.000 title abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 85
- 238000007710 freezing Methods 0.000 claims abstract description 55
- 230000008014 freezing Effects 0.000 claims abstract description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims description 45
- 238000012216 screening Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 230000005484 gravity Effects 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000003672 processing method Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 description 31
- 229910052744 lithium Inorganic materials 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- -1 hydrogen ions Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000012267 brine Substances 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000010892 electric spark Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KOAWAWHSMVKCON-UHFFFAOYSA-N 6-[difluoro-(6-pyridin-4-yl-[1,2,4]triazolo[4,3-b]pyridazin-3-yl)methyl]quinoline Chemical compound C=1C=C2N=CC=CC2=CC=1C(F)(F)C(N1N=2)=NN=C1C=CC=2C1=CC=NC=C1 KOAWAWHSMVKCON-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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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- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
The invention relates to a treatment method for recycling waste batteries, which comprises the following steps: freezing a battery pack including a battery containing a plurality of lithium ions as unit cells by cooling for a minimum cooling time or more that satisfies the following formula 1; and crushing the frozen battery pack.<1 (1)>Shortest cooling time=a× (W 0.33 )A＝4×e (‑0.02×dT) W=battery weight (Kg), dt= -external cooling temperature-target temperature-and-represents absolute value.
Description
Technical Field
The invention relates to a waste battery and provides a treatment method for reutilization of the waste battery.
Background
The application field of lithium secondary batteries is very wide, and the use thereof is gradually expanding from small electronic instruments to automobiles.
These lithium secondary batteries have a reduced charge capacity after use for more than 5 years and 10 years, and cannot be used any more. Therefore, the problem of disposal of batteries that cannot be used any more is becoming a social problem in countries around the world.
A lithium secondary battery generally includes a positive electrode including Ni, co, mn, etc. in addition to lithium, a negative electrode including a nonaqueous organic solvent, and an electrolyte including Li, ni, co, mn, etc. which are expensive elements, because the organic solvent may be a fire hazard, and research into recycling these elements from waste batteries is actively underway.
In particular, in the field of using these lithium secondary batteries, the popularity of electric vehicles is increasing, which require high output and are used in the form of a battery pack (fig. 1) in which one or more battery modules (modules) of 20V to 60V are connected in series and one or more unit cells (cells) of 2V to 4V are connected in series/parallel, and thus research on recycling Li, ni, co, mn and the like from such battery packs has been attracting attention.
In order to recycle the lithium secondary battery, the battery must be disassembled, but the disassembly (i.e., destruction) of the battery pack or battery module level has a problem of causing fire. Therefore, in order to avoid such problems, battery disassembly employs the following method: as shown in fig. 2, the battery is discharged, and then the battery pack is physically disassembled into a battery module and unit cells and is completely discharged in brine, and then calcined, crushed, and gravity-screened to obtain Black powder (Black power), i.e., a mixture of positive electrode material and negative electrode material powder. However, this method has a problem of environmental pollution because hydrogen ions of the electrolyte solvent are combined with ions of the electrolyte salt (e.g., fluorine ions) to generate harmful gas Hydrogen Fluoride (HF) during discharge of the brine, and water quality pollution may be caused due to discharged wastewater containing chlorine ions after discharge of the brine.
Further, these processes are not suitable for practical use because of the problem that the entire process time is too long, for example, for the battery packs, discharge of each battery pack takes 8 hours, physical disassembly takes 1 to 2 hours on average, brine discharge takes about 24 hours, and crushing and gravity screening processes take about 1 hour.
Thus, there is a need for a simpler method of disassembling batteries, particularly battery packs.
Disclosure of Invention
Technical problem
The present invention aims to provide a treatment method for recycling waste batteries, which can stably crush a battery pack with a simple process without explosion and fire.
Technical proposal
The battery processing method according to an embodiment of the present invention may include the steps of: freezing a battery pack including a battery containing a plurality of lithium ions as unit cells by cooling for a minimum cooling time or more that satisfies the following formula 1; and crushing the frozen battery pack.
< 1>
Shortest cooling time=a× (W 0.33 )
A＝4×e (-0.02×dT) W=battery weight (Kg), dt= -external cooling temperature-target temperature-and-represents absolute value.
In one embodiment, the freezing step may be performed as cooling to-150 ℃ to-60 ℃. In one embodiment, the freezing step may be performed by cooling to-60 ℃ to-20 ℃, and the crushing step may be performed under the supply of inert gas, carbon dioxide, nitrogen, water, or a combination thereof.
In one embodiment, the freezing step may be performed by cooling to-60 ℃ to-20 ℃ and the crushing step may be performed under vacuum ambient conditions below 100torr. In one embodiment, the crushing step may be carried out until the maximum size of the crushed product is 10mm or less.
In one embodiment, after the crushing step, the method may further comprise the step of: magnetic screening or gravity screening for separating products with a maximum size of 1mm or less. In one embodiment, after the freezing step and before the crushing step, the method may further comprise performing the steps of: and extruding the frozen battery pack. In one embodiment, the extrusion process may be performed to a thickness of 1/2 or less of the thickness of the battery pack before the freezing.
A battery processing method according to another embodiment of the present invention may include the steps of: the battery pack including the battery containing a plurality of lithium ions as the unit cells is cooled for a minimum cooling time or longer satisfying the following formula 1, and is crushed.
< 1>
Shortest cooling time=a× (W 0.33 )
A＝4×e (-0.02×dT) W=battery weight (Kg), dt= -external cooling temperature-target temperature-and-represents absolute value.
In one embodiment, the freezing step may be performed as cooling to-150 ℃ to-60 ℃. In one embodiment, the freezing step may be performed by cooling to-60 ℃ to-20 ℃, and the crushing step may be performed under the supply of inert gas, carbon dioxide, nitrogen, water, or a combination thereof.
In one embodiment, the freezing step may be performed by cooling to-60 ℃ to-20 ℃ and the crushing step may be performed under vacuum ambient conditions below 100torr.
In one embodiment, the crushing step may be carried out until the maximum size of the crushed product is 10mm or less. In one embodiment, after the crushing step, the method may further comprise the step of: magnetic screening or gravity screening for separating products with a maximum size of 1mm or less.
Effects of the invention
According to the disposal method for the recycling of the waste battery according to one embodiment of the present invention, the waste battery can be disposed of in a short time with a simple process by the relationship of the shortest holding time in the refrigerator according to the weight of the battery, and there is no risk of explosion and fire when the battery breaks.
Drawings
Fig. 1 is a schematic diagram simply illustrating the structures of unit cells, modules, and a battery pack.
Fig. 2 is a process diagram schematically showing a conventional waste battery treatment process.
Fig. 3 is a schematic diagram schematically illustrating a processing method for recycling waste batteries according to one embodiment.
Fig. 4 is a graph of voltage change based on the implementation of the battery pack freezing process according to example 1.
Fig. 5 is a photograph of the crushed product according to example 1.
FIG. 6 is a photograph of a fire generated in the crushing step of comparative example 1.
FIG. 7 is a graph for a shortest cooling time according to one embodiment of the present invention.
Fig. 8a and 8b are photographs of an embodiment of the shortest cooling time according to the present invention, and fig. 8c and 8d are photographs of a comparative example of the shortest cooling time according to the present invention.
Detailed Description
The terms first, second, third, etc. are used to describe various parts, components, regions, layers and/or sections and these parts, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one portion, component, region, layer and/or section from another portion, component, region, layer and/or section. Accordingly, a first portion, component, region, layer and/or section discussed below could be termed a second portion, component, region, layer and/or section without departing from the scope of the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular is intended to include the plural unless the context clearly dictates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, regions, integers, steps, actions, elements, and/or components, but do not preclude the presence or addition of other features, regions, integers, steps, actions, elements, and/or components.
If a portion is described as being above another portion, then there may be other portions directly above or between the other portions. When a portion is described as directly above another portion, there are no other portions therebetween.
Although not otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms defined in the dictionary should be interpreted as having meanings consistent with the relevant technical literature and the disclosure herein, and should not be interpreted in an idealized or overly formal sense.
Hereinafter, embodiments of the present invention will be described in detail. However, the following embodiments are examples, and the present invention is not limited to the following embodiments, but the scope of the present invention is defined by the claims.
A treatment method for recycling waste batteries according to one embodiment includes the steps of: freezing a battery pack including a battery containing a plurality of lithium ions as unit cells for a minimum cooling time or longer; and crushing the frozen battery pack. The lithium ion-containing battery may include various lithium ion-containing batteries, and may be, for example, a lithium secondary battery separated from an automobile, a secondary battery separated from an electronic device such as a mobile phone, a camera, a notebook computer, or the like, and may be, in particular, a lithium secondary battery.
In the step of cooling a battery pack including a plurality of lithium ion-containing batteries as unit cells for a minimum cooling time or longer for the treatment method for recycling the waste batteries, the minimum cooling time may satisfy the following formula 1, and the battery pack may be cooled for freezing at least the value of the following formula 1.
< 1>
Shortest cooling time=a× (W 0.33 )
A＝4×e (-0.02×dT) W=battery weight (Kg), dt= -external cooling temperature-target temperature-and-represents absolute value.
The shortest cooling time of the above formula 1 is a function of the weight of the battery pack (specifically, the weight of the battery), the external cooling temperature (the cooling temperature applied to the battery pack to cool the battery pack), and the target temperature (for cooling the battery pack, specifically, the electrolyte within the battery pack). The step of freezing the battery pack has an advantage in that the electrolyte inside the battery pack can be cooled by cooling the battery pack for the minimum cooling time or longer, thereby stably performing the subsequent process. For the step of freezing the battery pack, if the freezing time of the battery pack is less than the minimum cooling time, the electrolyte is not cooled, and there is a risk that a fire may occur when broken.
For the freezing process according to one embodiment, it may be performed at a sufficient temperature to freeze the electrolyte, for example, it may be performed to cool to-150 ℃ (minus 150 ℃) to-60 ℃ (minus 60 ℃). If the battery pack is cooled to the temperature range, the voltage slightly remaining inside the battery, for example, a voltage of about 2V to 3V, is generally reduced to approximately 0V, as shown in fig. 2, so that even if a short circuit in which the positive electrode and the negative electrode are in direct contact occurs, no battery reaction occurs, so that the temperature of the battery does not rise, and the electrolyte does not generate gas and burn. In addition, since the electrolyte is in a frozen state, mobility of lithium ions is low, and an energization characteristic due to lithium ion migration is remarkably lowered, vaporization of the electrolyte does not occur, and thus a combustible gas such as ethylene, propylene, hydrogen, or the like is not generated.
If the freezing step is beyond the above temperature range, for example, cooled to a temperature higher than-60 ℃, the voltage remaining inside the battery is not reduced to 0V, and a battery reaction due to a short circuit may occur, so that the electrolyte is not completely frozen, which is not preferable. In addition, if cooled to-150 ℃, the electrolyte will freeze sufficiently and the internal voltage of the battery will drop to 0V, thus eliminating the need to drop to a temperature below-150 ℃.
In another embodiment, the freezing process may also be performed to cool to a temperature capable of inhibiting vaporization of the electrolyte, for example-60 ℃ (zero 60 ℃) to-20 ℃ (zero 20 ℃).
If the freezing step is performed by cooling to-60 ℃ (60 ℃ below zero) to-20 ℃ (20 ℃ below zero), the crushing step may be performed under the condition of supplying inert gas, carbon dioxide, nitrogen, water or a combination thereof or under the vacuum environment condition of 100torr or less.
The inert gas may be argon, helium or mixtures thereof. The vacuum environment pressure is below 100torr, and may be 0.00001 (10) -5 ) torr to 100torr.
As described above, even if the freezing step is performed at a slightly higher temperature, for example, -60 ℃ to-20 ℃, the crushing step is performed by supplying inert gas, carbon dioxide, nitrogen, water or a combination thereof or by adjusting the pressure to 100torr or less in a vacuum atmosphere. Therefore, since the supply of oxygen is suppressed, the reaction of the electrolyte with oxygen can be prevented, and the resulting explosion can be prevented, and also the vaporization of the electrolyte can be suppressed, so that the generation of combustible gases such as ethylene, propylene, hydrogen, and the like can be avoided.
If the freezing step is carried out at-60 to-20 ℃, there is a possibility that a voltage remains in the battery pack when the freezing step is carried out in an air atmosphere or at a pressure of more than 100torr, and since the electrolyte is not frozen, there is a possibility that an electric spark generated when a short circuit occurs due to the remaining voltage causes the electrolyte to evaporate, and this is not preferable.
As described above, the treatment method for recycling the waste battery includes the steps of: before the battery pack including the battery, such as a lithium secondary battery, is broken, the battery pack is frozen, so that stability can be ensured to avoid a fire risk that may occur during the breaking of the battery pack.
The step of crushing the frozen battery pack may be a step of applying impact or pressure to the battery pack to detach a part of the battery pack from the battery pack. The step of crushing the frozen battery pack according to one embodiment may also be a process of crushing the battery pack, a process of cutting the battery pack, a process of compressing the battery pack, and combinations thereof. Specifically, the breaking process may be all processes in which the battery pack is broken to obtain a small size.
The step of crushing the frozen battery pack according to one embodiment may include any process of compressing the frozen battery pack or applying an external force such as a shearing force, a stretching force, or the like to crush the frozen battery pack. For example, the crushing step may be carried out using a crusher.
As described above, the treatment method according to one embodiment does not physically disassemble the battery pack into the battery module and the unit cells, but performs the process of crushing the battery pack itself, so that the process is simple, a large number of batteries are frozen at a time during the freezing process, and thus, the waste batteries can be treated in a short time for recycling. In addition, in the case of an electric vehicle using a battery pack as an energy source, the treatment method according to one embodiment may also be employed after disassembly into a battery pack form from the vehicle, so that the battery pack can be stably treated through a simple process.
In general, when a battery pack is directly broken, explosion and fire may occur due to an electrolyte contained therein, and particularly, when a specific pressure is applied to the battery pack, a separator is physically broken, short-circuit occurs to form a high current, and thus an electric spark is generated, and the electrolyte fires and may cause a fire due to the electric spark.
In one embodiment, the battery pack is frozen to suppress ignition of the liquid electrolyte contained in the battery pack, and then the breaking process is performed, so that problems caused by ignition of the electrolyte do not occur.
For such a crushing step, it is possible to perform the crushing to a maximum size of the crushed product of 10mm or less, for example, 0.1mm to 10mm. If the crushing step is performed under such conditions, a separation step such as magnetic force screening or specific gravity screening of the crushed product or the like can be effectively applied, and finally, a powder of the positive electrode material and the negative electrode material, such as black powder, mixed with the positive electrode active material and the positive electrode current collector, and the negative electrode material of the negative electrode current collector can be more easily obtained. Meanwhile, if the crushing process is performed under such conditions, the electrolyte can be more easily removed from the crushed product.
The crushing step may be performed at least once or more. Specifically, the crushing step may be performed at least once continuously or discontinuously.
Since the crushed product is in a room temperature state, the electrolyte can be changed into a liquid state again along with the temperature rise, but from the moment of crushing, the positive electrode material and the negative electrode material contained in the crushed product become electrode ions in an equilibrium state, short circuits can not occur, and when the temperature of the electrolyte reaches the room temperature, the crushed product can be kept stable.
In one embodiment, the step of extruding the frozen battery pack may be further performed after the freezing step and before the crushing step. The extrusion process may be performed to a thickness of less than 1/2, such as 1/50 to 1/2, of the thickness of the battery pack prior to freezing. If the pressing process is further performed, the crushing process can be more uniformly performed. For example, the material can be stably supplied without deviation to the inside of a crusher used in the crushing process.
If the pressing process is performed to have a thickness greater than 1/2 of the thickness of the battery pack before freezing, it is difficult to form a certain shape, and thus there is a possibility that the time of the crushing process becomes long.
Then, a step of separating a product having a maximum size of 1mm or less from the crushed product may be further performed. The separation step may be performed by magnetic screening or gravity screening, and any screening procedure well known in the art may be employed. As the separation step is further performed in this manner, a powder in which the positive electrode active material and the negative electrode active material are mixed with the positive electrode current collector and the negative electrode current collector can be obtained. In one embodiment, after the crushing step, a step of removing and separating the electrolyte may be performed. For the electrolyte removal process, the crushed product may be removed by heat treatment or vacuum drying.
According to another embodiment of the treatment method, the freezing and crushing steps may also be performed together. Specifically, the treatment method may comprise the steps of: freezing and crushing a battery pack including a battery containing a plurality of lithium ions as unit cells. At this time, in the freezing step, the frozen state is maintained for a minimum cooling time or longer that satisfies the following formula 1, and then the crushing step may be performed while maintaining the frozen state.
< 1>
Shortest cooling time=a× (W 0.33 )
A＝4×e (-0.02×dT) W=battery weight (Kg), dt= -external cooling temperature-target temperature-and-represents absolute value.
By simultaneously performing the freezing and crushing processes, the process steps can be simplified, thereby ensuring economic benefits.
In one embodiment, the freezing step may be performed as cooling to-150 ℃ to-60 ℃. In the above treatment method, the battery pack may be frozen to-60 to-20 ℃ and subjected to the crushing step under the supply of an inert gas, carbon dioxide, nitrogen, water, or a combination thereof, or the battery pack may be frozen to-60 to-20 ℃ and subjected to the crushing step under the vacuum condition of 100torr or less. To the extent not inconsistent, the detailed description is the same as the previous disclosure.
In one embodiment, the step of freezing and crushing may further comprise performing the steps of: magnetic screening or gravity screening for separating products with a maximum size of 1mm or less. The content of the freezing and crushing steps may be referred to as the above-described content insofar as they are not contradictory.
Examples of the present invention and comparative examples are described below. However, the following embodiment is only one embodiment of the present invention, and the present invention is not limited to the following embodiment.
Example 1 ]
Freezing a battery pack to-80 deg.c, the battery pack comprising unit cells, the unit cell contains a material containing LiNi 0.6 Co 0.2 Mn 0.2 O 2 Positive electrode containing positive electrode active material, negative electrode containing artificial graphite negative electrode active material, and electrolyte. The electrolyte uses a mixed solvent of dimethyl carbonate and diethyl carbonate (50:50 volume ratio), wherein 1.0M LiPF is dissolved 6 。
The results of measuring the cell voltage when the battery was frozen to-80 ℃ are shown in fig. 4. As shown in fig. 4, the battery pack showed almost the same voltage at a high temperature of about 40 c, at room temperature and at a temperature up to-60 c, and thus it was found that the battery characteristics were not lost. Then, when the temperature was lowered from-60℃to-70℃the voltage was rapidly lowered, and the result of the voltage at-70℃being 0 was obtained, whereby it was found that the battery pack did not suffer from short circuit when frozen to-60℃to-150 ℃.
Crushing the frozen battery pack by using a shear crusher. The crushing step is performed such that the maximum size of the crushed product is 10mm or less. A photograph of the crushed product is shown in fig. 5.
And (3) carrying out specific gravity screening on the crushed product, thereby obtaining a product with the maximum size of less than 1 mm.
Comparative example 1 ]
The battery pack used in example 1 was crushed using the same crusher as in example 1 without freezing. A flame caused by the short circuit is generated during the breaking process, as shown in fig. 6.
As described above, it was confirmed that there was excellent stability by example 1 and comparative example 1, since short circuit and flame generation did not occur in the battery breaking step by the step of freezing the battery pack including the battery before the battery breaking.
FIG. 7 is a graph for a shortest cooling time according to one embodiment of the present invention.
Referring to fig. 7, it can be confirmed that the shortest cooling time for cooling the battery in the battery pack freezing step can be derived according to the battery processing method of one embodiment of the present invention. Specifically, it was confirmed that the shortest cooling time was related to the battery weight, the external cooling temperature, and the target temperature.
Fig. 7 shows the external cooling temperature and the shortest cooling time when the target temperature was set to-70 deg.c and the battery weights were 2.5kg (a), 10kg (B), 20kg (C) and 50kg (D), respectively. When the battery is cooled, the electrolyte of the battery starts to cool after a predetermined time passes, and the voltage becomes 0. It was confirmed that the battery was cooled with a minimum holding time required for sufficient cooling to the inside (specifically, the electrolyte).
Specifically, in a heat transfer state for cooling in which heat is lost to the outside, if the specific heat of the battery itself is taken into consideration, the battery weight and the time for cooling are required. Even in a heat transfer state for cooling in which heat is lost to the outside, the battery weight and the time for cooling are required in consideration of the specific heat of the battery itself.
As described above, in the present invention, in order to cool the battery, the minimum time required for cooling can be confirmed using the external cooling temperature for freezing, the target temperature, and the battery weight.
The shortest cooling time based on the battery weight, the external cooling temperature is recorded in table 1 below.
[ Table 1 ]
From table 1 above, it is confirmed that the smaller the battery weight is, the smaller the shortest cooling time of the battery as a cooling target is. When the value of formula 1 derived from the relational expression based on the battery weight, the external cooling temperature, and the target temperature is cooled as the shortest cooling time, it can be confirmed that the battery (specifically, the electrolyte of the battery) is cooled. In addition, when the battery is cooled for a time equal to or longer than the value of the above formula 1, a fire does not occur during the battery pulverization in the subsequent steps. Fig. 8a and 8b are photographs of an embodiment of the shortest cooling time according to the present invention, and fig. 8c and 8d are photographs of a comparative example of the shortest cooling time according to the present invention.
Referring to fig. 8a and 8b, the state of fire occurrence of broken objects in which the cooling time during battery cooling is less than the minimum cooling time required was examined. In the above experiment, the battery weight was 25kg, and the value of the following formula 1 was 7 hours at the external cooling temperature of-95℃and the target freezing temperature of-70℃for 5 hours, which was less than the value of the following formula 1.
< 1>
Shortest cooling time=a× (W 0.33 )
A＝4×e (-0.02×dT) W=battery weight (Kg), dt= -external cooling temperature-target temperature-and-represents absolute value.
Referring to fig. 8c and 8d, the fire occurrence state of the crushed material when the minimum freezing time required for cooling the battery by freezing is more than the minimum freezing time was examined. In the experiments, the battery weight, external cooling temperature were the same as in fig. 8a and 8b, and the shortest freezing time was 7 hours or more.
Table 2 below compares the fire occurrence status of the examples and comparative examples based on the same battery weight, external cooling temperature and shortest freezing time according to fig. 8a to 8 d. For the determination of the fire occurrence status, after the battery is broken, if a fire is observed, it is denoted as "O", otherwise it is denoted as "X".
[ Table 2 ]
From table 2 above, it is confirmed that if the battery cooling time is less than the value of equation 1 corresponding to the shortest cooling time, the battery is not cooled to the electrolyte, and thus a fire occurs after the battery breaks. As described above, when the battery is cooled with the value of equation 1 set to the shortest cooling time, the broken battery is broken, and no fire occurs, so that the broken material can be stably utilized.
The present invention can be implemented in various ways and is not limited to the embodiments described, and it will be understood by those skilled in the art that the present invention can be implemented in other specific ways without changing the technical idea or essential features of the invention. Accordingly, it should be understood that the above-described embodiments are illustrative in all respects, and are not intended to limit the present invention.
Claims (14)
1. A battery processing method, comprising the steps of:
freezing a battery pack including a battery containing a plurality of lithium ions as unit cells by cooling for a minimum cooling time or more that satisfies the following formula 1; and
crushing the frozen battery pack,
< 1>
Shortest cooling time=a× (W 0.33 )
A＝4×e (-0.02×dT) W=battery weight (Kg), dt= -external cooling temperature-target temperature-and-represents absolute value.
2. The process according to claim 1, wherein,
the freezing step is carried out by cooling to-150 ℃ to-60 ℃.
3. The process according to claim 1, wherein,
the freezing step is carried out by cooling to-60 ℃ to-20 ℃,
the crushing step is carried out under the supply of inert gas, carbon dioxide, nitrogen, water or a combination thereof.
4. The process according to claim 1, wherein,
the freezing step is carried out by cooling to-60 ℃ to-20 ℃,
the crushing step is carried out under vacuum environment conditions below 100torr.
5. The process according to claim 1, wherein,
the crushing step is carried out until the maximum size of the crushed product is below 10mm.
6. The process according to claim 1, wherein,
after the crushing step, further comprising the step of: magnetic screening or gravity screening for separating products with a maximum size of 1mm or less.
7. The process according to claim 1, wherein,
the method further comprises the following steps after the freezing step and before the crushing step: and extruding the frozen battery pack.
8. The process according to claim 7, wherein,
the extrusion step is performed so that the thickness of the battery pack before freezing is 1/2 or less.
9. A battery processing method, comprising the steps of:
freezing a battery pack including a plurality of lithium ion-containing batteries as unit cells for a minimum cooling time or longer satisfying the following formula 1, and crushing the battery pack,
< 1>
Shortest cooling time=a× (W 0.33 )
A＝4×e (-0.02×dT) W=battery weight (Kg), dt= -external cooling temperature-target temperature-and-represents absolute value.
10. The process according to claim 9, wherein,
the freezing step is carried out by cooling to-150 ℃ to-60 ℃.
11. The process according to claim 9, wherein,
the freezing step is carried out by cooling to-60 ℃ to-20 ℃,
the crushing step is carried out under the supply of inert gas, carbon dioxide, nitrogen, water or a combination thereof.
12. The process according to claim 9, wherein,
the freezing step is carried out by cooling to-60 ℃ to-20 ℃,
the crushing step is carried out under vacuum environment conditions below 100torr.
13. The process according to claim 9, wherein,
the crushing step is carried out until the maximum size of the crushed product is below 10mm.
14. The process according to claim 9, wherein,
after the crushing step, further comprising the step of: magnetic screening or gravity screening for separating products with a maximum size of 1mm or less.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2021-0040649 | 2021-03-29 | ||
| KR10-2022-0033750 | 2022-03-18 | ||
| KR1020220033750A KR102729469B1 (en) | 2021-03-29 | 2022-03-18 | Method of treating waste battery reuse |
| PCT/KR2022/004402 WO2022211446A1 (en) | 2021-03-29 | 2022-03-29 | Processing method for reusing waste battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117256065A true CN117256065A (en) | 2023-12-19 |
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|---|---|---|---|
| CN202280025696.6A Pending CN117256065A (en) | 2021-03-29 | 2022-03-29 | Treatment method for recycling waste batteries |
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| Country | Link |
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| CN (1) | CN117256065A (en) |
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