Processing method for recycling waste batteries

Abstract

To provide a processing method for recycling waste batteries.SOLUTION: The method includes a step for cooling and freezing a battery pack containing multiple lithium-ion batteries as unit cells for at least the minimum cooling time satisfying Equation 1, and a step for crushing the frozen battery pack. <Formula 1> Minimum Cooling Time=A×(W0.33) Where: A=4×e(-0.02×dT), W=Battery Weight (Kg), dT=|External Cooling Temperature-Target Temperature|, and II denotes the absolute value.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] This relates to waste batteries and provides a processing method for recycling waste batteries. be. [Background technology]

[0002] Lithium secondary batteries are used in a wide range of fields, from small electronic devices to automobiles. The range of uses is gradually expanding.

[0003] These lithium secondary batteries can be recharged after a minimum of 5 years and a maximum of 10 years of use. The capacity of the electricity supply has decreased and it is no longer possible to use it. The issue of pond disposal has become a social problem.

[0004] Lithium secondary batteries generally contain lithium, as well as a positive electrode containing Ni, Co, Mn, etc. It contains a negative electrode and an electrolyte containing a non-aqueous organic solvent, and the organic solvent may cause a fire. In addition, the Li, Ni, Co, Mn, etc. contained in the positive electrode are expensive elements, so Therefore, research into recycling these materials is being actively carried out.

[0005] In particular, among the fields in which such lithium secondary batteries are used, the popularity of electric vehicles is increasing. However, because such electric vehicles require high output, 2V or 4V A 20V to 60V battery module consisting of one or more unit cells connected in series or parallel. A battery pack consisting of one or more modules connected in series. ) form (Fig. 1), so Li, Ni, Co, Mn, etc. are extracted from such battery packs. Research into recycling these materials is attracting attention.

[0006] In order to recycle lithium secondary batteries, the batteries must be disassembled, but the packs themselves Disassembly of the battery and module, i.e. destruction, can cause fires. To prevent this, as shown in Figure 2, after the battery is electrically discharged, The battery pack was physically disassembled into modules and cell subunits, and then fully discharged in salt water. After that, the mixture is calcined, crushed and gravity-separated to obtain a black powder mixture of the positive and negative electrode materials. The method of obtaining black power is to disassemble the battery. One method is to dissolve hydrogen ions of the electrolyte solvent and ions of the electrolyte salt, such as fluorine ions, during discharge of salt water. The ions combine to produce the harmful gas hydrogen fluoride (HF), which causes environmental pollution. There is a problem, and after saltwater discharge, the wastewater containing chloride ions is discharged, which causes water pollution. This can cause problems.

[0007] In addition, this process requires that the electrical discharge last for 8 hours per battery pack. Physical decomposition takes an average of 1 to 2 hours, salt water discharge takes about 24 hours, and crushing and specific gravity The sorting process takes about an hour, so the overall process time is too long. There are problems with this and it is not suitable for practical application.

[0008] Therefore, there is a demand for a method for more easily disassembling batteries, especially battery packs. do. Summary of the Invention [Problem to be solved by the invention]

[0009] The method for recycling waste batteries according to one embodiment of the present invention is simple and free from explosions and fires. To provide a processing method for recycling waste batteries that can stably crush battery packs in a simple process. This is what we should do. [Means for solving the problem]

[0010] A battery treatment method according to an embodiment of the present invention is a method for treating a battery containing a plurality of lithium ions. The battery pack containing the unit battery is cooled for a minimum cooling time that satisfies the following formula 1. and crushing the frozen battery pack. .

[0011] <Expression 1> Minimum cooling time = A × (W 0.33 ) (A=4×e (-0.02×dT) , W = battery weight (kg), dT = │ external cooling Temperature - target temperature ||| means absolute value.)

[0012] In one embodiment, the freezing step is performed by cooling to a temperature between -150°C and -60°C. In one embodiment, the freezing step is carried out at a temperature below -60°C. The crushing step is carried out by cooling the mixture at -20°C, and the crushing step is carried out in an inert gas, carbon dioxide, nitrogen, The process may be carried out under conditions in which water or a combination thereof is supplied.

[0013] In one embodiment, the freezing step is carried out at a temperature between -60°C and -20°C. The crushing step is carried out under a vacuum atmosphere of 100 torr or less. In one embodiment, the crushing step may be performed such that the maximum size of the crushed product is 1 This may be continued until the thickness reaches 0 mm or less.

[0014] In one embodiment, after the crushing step, the raw material has a maximum size of 1 mm or less. The method may further include a step of magnetic separation or gravity separation to separate the components. In an embodiment, after the freezing step and before the crushing step, the frozen In one embodiment, the method may further include a step of crimping the assembled battery pack. The crimping step is carried out so that the thickness of the battery pack is half or less of the thickness before freezing. This may also be the case.

[0015] A battery treatment method according to another embodiment of the present invention includes treating a battery containing a plurality of lithium ions. The battery pack containing the unit battery is cooled for a minimum cooling time that satisfies the following formula 1. The method may include the step of crushing the battery pack while freezing it.

[0016] <Expression 1> Minimum cooling time = A × (W 0.33 ) (A=4×e (-0.02×dT) , W = battery weight (kg), dT = │ external cooling Temperature - target temperature ||| means absolute value.)

[0017] In one embodiment, the freezing step is performed by cooling to a temperature between -150°C and -60°C. In one embodiment, the freezing step is carried out at a temperature below -60°C. The crushing step is carried out by cooling the mixture at -20°C, and the crushing step is carried out in an inert gas, carbon dioxide, nitrogen, The process may be carried out under conditions in which water or a combination thereof is supplied.

[0018] In one embodiment, the freezing step is carried out at a temperature between -60°C and -20°C. The crushing step is carried out under a vacuum atmosphere of 100 torr or less. That's fine.

[0019] In one embodiment, the crushing step is carried out to crush the material so that the maximum size of the crushed product is 10 mm or more. In one embodiment, after the crushing step, Next, a magnetic or gravity separation step is carried out to separate products with a maximum size of 1 mm or less. The process may further include the step of [Effects of the Invention]

[0020] The method for recycling waste batteries according to one embodiment of the present invention is Due to the minimum maintenance time in the refrigerator, there is a risk of explosion and fire when the battery is crushed. The process is simple and non-hazardous, allowing waste batteries to be disposed of in a short time. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 is a schematic diagram showing the unit cell, module, and battery pack structure in a simplified manner. [Figure 2] FIG. 2 is a process diagram that schematically shows a conventional waste battery treatment process. [Figure 3] FIG. 3 is a schematic diagram illustrating a processing method for recycling waste batteries according to one embodiment. [Figure 4] FIG. 4 is a graph showing voltage changes during the freezing process of the battery pack frozen according to Example 1. [Figure 5] FIG. 5 is a photograph of the crushed product according to Example 1. [Figure 6] FIG. 6 is a photograph of Comparative Example 1, showing ignition during the crushing process. [Figure 7] FIG. 7 is a graph showing the minimum cooling time according to one embodiment of the present invention. [Figure 8] 8a and 8b are photographs of an example with the minimum cooling time of the present invention, and FIGS. 8c and 8d are photographs of a comparative example with the minimum cooling time of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0022] Terms such as first, second and third refer to various parts, components, regions, layers and / or sections. These terms are used to describe, in part, Distinguishing a component, region, layer, or section from another component, region, layer, or section Therefore, the first part, component, region, layer or A section may be a second part, component, region, layer or section without departing from the scope of the present invention. It is sometimes referred to as a ction.

[0023] The terminology used herein is merely to refer to particular embodiments and is not intended to be limiting of the present invention. The singular forms "a," "an," and "the" used herein are intended to clarify the term. "comprises" as used in the specification means: It embodies specific properties, regions, integers, steps, operations, elements and / or components and The presence or addition of any property, region, integer, step, operation, element and / or component is not excluded. It's not that.

[0024] When we say that one part is "on" or "above" another part, this means that the other part "on" or "above" or there can be other parts between them. When we say that a part is "directly on top of" another part, there are no other parts in between. .

[0025] All terms, including technical and scientific terms, used herein without being otherwise defined are intended to be illustrative and not restrictive. The meanings are the same as those generally understood by a person skilled in the art to which the present invention pertains. Terms defined in commonly used dictionaries have a single meaning. Unless additionally interpreted and defined to have a meaning consistent with the content of the and not interpreted in a very formal sense.

[0026] DETAILED DESCRIPTION OF THE INVENTION The present invention will now be described in detail by way of example only. The present invention is not limited by these claims, and the present invention is not limited by these claims. It is only defined by the range of categories.

[0027] In one embodiment, a method for recycling waste batteries is provided. A battery pack including a battery as a unit battery is cooled and frozen for a minimum cooling time or longer. and crushing the frozen battery pack. The batteries may include various types of batteries, including lithium ion, e.g., automotive Lithium secondary batteries separated from electronic devices such as mobile phones, cameras, and laptops It may be a secondary battery, specifically a lithium secondary battery, separated from the device.

[0028] The method for recycling waste batteries is to divide a plurality of lithium-ion batteries into unit batteries. a step of cooling and freezing the battery pack including the battery pack for a minimum cooling time or more, The cooling time can satisfy the following formula 1, and the battery pack is cooled to a value equal to or greater than the value of the following formula 1. The product can be frozen.

[0029] <Expression 1> Minimum cooling time = A × (W 0.33 ) (A=4×e (-0.02×dT) , W = battery pack weight (kg), dT = | external cooling Temperature - target temperature ||| means absolute value.)

[0030] The minimum cooling time in the above formula 1 depends on the weight of the battery pack, specifically the weight of the battery, an external cooling temperature, which is the cooling temperature applied to the battery pack for pack cooling; The battery pack specifically means a target temperature for cooling the electrolyte in the battery pack. The step of freezing the battery pack is performed for a period of time equal to or longer than the minimum cooling time. The electrolyte inside the battery pack is cooled, and subsequent processes can be carried out stably. The step of freezing the battery pack has an advantage of being able to cool the battery pack for a period of time that is shorter than the minimum cooling time. If the battery pack is frozen for a short period of time, the electrolyte will not be cooled, and there is a risk of fire when it is crushed. There is a problem that can occur.

[0031] The freezing step according to one embodiment may be carried out at a temperature sufficient to freeze the electrolyte. For example, cooling may be performed at -150°C (minus 150°C) or -60°C (minus 60°C). When the battery pack is cooled within the above temperature range, the minute amount of voltage remaining inside the battery, e.g. For example, a voltage of approximately 2V to 3V drops to nearly 0V, as shown in Figure 2. Therefore, even if a short circuit occurs where the positive and negative electrodes come into direct contact, no battery reaction occurs. The electrolyte does not increase, and gas generation and combustion do not occur. Therefore, the mobility of lithium ions is very low, and the current-carrying characteristics due to the movement of lithium ions are notable. Since the electrolyte does not evaporate, it is suitable for use with ethylene, propylene, hydrogen, etc. No flammable gases may be generated.

[0032] If the freezing step is outside the above temperature range, for example, cooling at a temperature higher than -60°C may be performed. In this case, the voltage remaining inside the battery does not drop to 0V, and a battery reaction occurs due to a short circuit. It is not suitable for cooling to -150°C because the electrolyte may not be completely frozen. Then, the electrolyte is frozen sufficiently and the internal voltage of the battery drops to 0V. There is no need to lower the temperature.

[0033] In another embodiment, the freezing step is carried out at a temperature capable of suppressing evaporation of the electrolyte solution, For example, the reaction may be carried out by cooling to -60°C (minus 60°C) to -20°C (minus 20°C).

[0034] When the freezing process is carried out at -60℃ (minus 60℃) or -20℃ (minus 20℃) The crushing process is carried out by supplying an inert gas, carbon dioxide, nitrogen, water or a combination thereof. The heating may be performed under conditions of a pressure of 100 torr or less, or under a vacuum atmosphere of 100 torr or less.

[0035] The inert gas may be argon gas, helium gas, or a mixture thereof. The pressure in the vacuum atmosphere is 100 torr or less, 0.00001 (10 -5 )tor The pressure may be between 100 torr and 100 torr.

[0036] In this way, even if the freezing process is carried out at a slightly higher temperature, such as -60°C or -20°C, the crushing The process may be carried out by supplying inert gas, carbon dioxide, nitrogen, water or a combination thereof, or by pressurizing. The pressure is adjusted to a vacuum atmosphere of 100 torr or less, so oxygen supply is suppressed. This prevents the electrolyte from reacting with oxygen, thereby preventing an explosion. This can suppress the evaporation of the electrolyte, and flammable materials such as ethylene, propylene, and hydrogen can be used. It does not generate sexual gases.

[0037] If the freezing process is carried out at -60°C or -20°C, it should be carried out in an air atmosphere or in a 100t If the pressure is too high, voltage may remain in the battery pack and the electrolyte may be damaged. Since the battery is not frozen, the remaining voltage will cause a spark to be generated in the event of a short circuit. This is not suitable as it may cause the electrolyte to vaporize and cause an explosion.

[0038] Thus, the processing method for recycling waste batteries is before crushing the battery pack, This ensures stability against the risk of fire that may occur during the construction process.

[0039] The step of crushing the frozen battery packs includes: This refers to a process of applying impact or pressure to the battery pack so that some of the battery pack breaks apart. The step of crushing the frozen battery pack according to the present invention includes a step of crushing the battery pack; It can refer to any of cutting, compressing, and combinations thereof. Specifically, the crushing process includes all the steps in which the battery packs are broken down into smaller pieces. means.

[0040] In one embodiment, the step of crushing the frozen battery pack comprises crushing the frozen battery pack. It may include all the steps of compressing the block or applying external forces such as shear force or tension force to destroy it. For example, the crushing step may be performed using a crusher.

[0041] In this way, the processing method according to one embodiment is a method of dividing a battery pack into modules and unit cells. The process is simple as the battery pack itself is crushed without being physically disassembled. By freezing a large number of batteries at once, waste batteries can be processed and recycled in a short time. In the case of electric vehicles that use a battery pack as an energy source, However, the battery pack can be separated from the automobile and the processing method according to the embodiment can be applied. This allows the battery pack to be safely disposed of through a simple process.

[0042] Generally, when a battery pack is directly crushed, there is a risk of explosion and fire due to the electrolyte contained in it. Damage may occur, especially if certain pressures are applied to the battery pack, which may physically damage the separator. When the battery is broken, a short circuit occurs, creating a high current and generating a spark. The electrolyte may ignite and cause a fire.

[0043] In one embodiment, the battery pack is frozen to prevent the development of liquid electrolyte contained in the battery pack. The crushing process is carried out after suppressing the fire, so there is no risk of electrolyte ignition. stomach.

[0044] Such a crushing process is carried out so that the maximum size of the crushed product is 10 mm or less, for example, 0.1 mm. If the crushing process is carried out under these conditions, the crushed product will Separation processes such as magnetic or gravity separation can be effectively applied to Positive electrode active material and positive electrode current collector positive electrode material, and negative electrode active material and negative electrode current collector negative electrode material Powders mixed with black powder are easier to In addition, when the crushing process is carried out under these conditions, the electrolyte can be easily extracted from the crushed product. can be removed.

[0045] The crushing step may be carried out at least once. It may be carried out continuously or discontinuously at least once or more times.

[0046] Since the crushed product is at room temperature, the electrolyte also increases in temperature, i.e., The positive and negative electrode materials are contained in the crushed product from the moment it is crushed, even though it turns into a liquid. In this case, the electrode ions are brought into equilibrium to the extent that short circuiting does not occur, and the electrolyte temperature is maintained at a constant level. When warmed, the crushed product can stabilize.

[0047] In one embodiment, after the freezing step and before the crushing step, A step of crimping the frozen battery pack may be further carried out. The thickness of the battery pack before the battery pack is reduced to 1 / 2 or less, for example, 1 / 50 to 1 / 2. If the crimping step is further carried out, the crushing step can be carried out more uniformly. For example, it is possible to supply the material to the crusher used in the crushing process without any variation. can be done.

[0048] When the crimping step is performed so that the thickness of the battery pack exceeds half of the thickness before freezing, In this case, it is difficult to create a consistent shape, which increases the time required for the crushing process. is possible.

[0049] Next, a step of separating products having a maximum size of 1 mm or less from the crushed products is performed. The separating step may be performed by magnetic separation or gravity separation. Any selection process well known in the art may be used. Then, by further performing a separation step, the positive electrode active material, the negative electrode active material, and the positive electrode current A powder in which the current collector and the negative electrode current collector are mixed can be obtained. In the method, after the crushing step, a step of removing the electrolyte and separating the particles may be carried out. The electrolyte removal step may involve heat treating the crushed product or vacuum drying it to remove the electrolyte.

[0050] In another embodiment of the processing method, the freezing and crushing steps may be carried out together. Specifically, the processing method is a battery pack including a plurality of lithium ion batteries as unit batteries. The method may further include a step of crushing the battery pack while freezing the battery pack. The freezing step maintains the frozen state for a minimum cooling time that satisfies the following formula 1, and After that, the frozen state may be maintained continuously and a crushing step may be carried out at the same time.

[0051] <Expression 1> Minimum cooling time = A × (W 0.33 ) (A=4×e (-0.02×dT) , W = battery weight (kg), dT = │ external cooling Temperature - target temperature ||| means absolute value.)

[0052] By carrying out the freezing and crushing steps simultaneously, the process steps are simplified and economical. It is possible to secure

[0053] In one embodiment, the freezing step is performed by cooling to a temperature between -150°C and -60°C. The treatment method may further include freezing the battery pack at a temperature between -60°C and -20°C. While supplying an inert gas, carbon dioxide, nitrogen, water or a combination thereof The crushing step may be carried out under a temperature of -60°C to -20°C. The crushing process may be carried out under a vacuum atmosphere of 100 torr or less. The explanations are the same as those given above to the extent that they are not inconsistent.

[0054] In one embodiment, after the step of crushing while freezing, the maximum size is 1 mm The method further comprises a step of magnetic separation or gravity separation to separate the product. The details of the freezing and crushing process may be referred to above to the extent that they are not inconsistent. It is possible. [Example]

[0055] Examples of the present invention and comparative examples are described below. However, the following examples are merely examples of the present invention. The following examples are merely illustrative and are not intended to limit the invention.

[0056] Example 1 LiNi 0.6 Co 0.2 Mn 0.2 The positive electrode contains O2 as the positive active material, and the negative electrode contains artificial graphite as the negative active material. The battery pack including the negative electrode containing the material and the unit cell containing the electrolyte was frozen at -80°C. The electrolyte is 1.0M LiPF6 dissolved in dimethyl carbonate and diethyl carbonate. A mixed solvent of ethanol and ethanol (50:50 volume ratio) was used.

[0057] The battery voltage was measured while the battery pack was frozen at -80°C. The results are shown in Figure 4. As shown in the figure, the battery pack can withstand temperatures as high as 40°C, room temperature, and temperatures as low as -60°C. The same voltage is displayed, so it is clear that the battery characteristics have not been lost. When the temperature drops from 0℃ to -70℃, the voltage drops sharply, and below -70℃ the voltage The result was 0, so if the battery pack is frozen at -60℃ or -150℃, It can be seen that no short circuit occurs.

[0058] The frozen battery packs were crushed using a shear crusher. The maximum size of the crushed product was 10 mm or less. Shown in Figure 5.

[0059] The crushed product was gravity separated to obtain products with a maximum size of 1 mm or less.

[0060] <Comparative Example 1> The battery packs used in Example 1 were crushed using the same crusher as in Example 1 without freezing. During the crushing process, a flame occurred due to a short circuit, as shown in Figure 6.

[0061] In this way, in Example 1 and Comparative Example 1, the battery was crushed before being crushed. The battery crushing step includes a step of freezing the battery pack containing the batteries. In this case, no short circuit occurs and no flame occurs, confirming excellent stability.

[0062] FIG. 7 is a graph showing the minimum cooling time according to one embodiment of the present invention.

[0063] Referring to FIG. 7, a battery treatment method according to an embodiment of the present invention includes freezing a battery pack. In the step of cooling the battery, a minimum cooling time for cooling the battery can be derived. Specifically, the minimum cooling time depends on the battery weight, the external cooling temperature, and the It can be seen that there is a correlation with the target temperature.

[0064] Figure 7 shows the battery weight when the target temperature is set at -70°C. g (A), 10 kg (B), 20 kg (C) and 50 kg (D), the external cooling temperature The temperature and minimum cooling time are shown. When the battery is cooled, the battery electrolyte After a certain time, cooling begins and the voltage becomes 0. In order to cool the battery sufficiently, the inside of the battery, specifically the electrolyte, It can be seen that a minimum maintenance time is required for

[0065] Specifically, in the heat transfer situation for cooling where heat is taken away from the outside, the specific heat of the battery itself is considered. When considering the battery weight and cooling time, it is important to consider the external Even in the heat transfer situation for cooling where heat is taken away, if we consider the specific heat of the battery itself, Battery weight and cooling time are required.

[0066] In this way, in the present invention, in order to cool the battery, an external cooling temperature for refrigeration is used. The minimum time required for cooling can be determined using the target temperature and battery weight.

[0067] Table 1 below lists the minimum cooling time depending on the battery weight and external cooling temperature. do.

[0068] [Table 1]

[0069] As can be seen from Table 1, the smaller the battery weight, the smaller the minimum battery size that needs to be cooled. It can be confirmed that the cooling time is even shorter. Also, the battery weight and external cooling temperature The value of Equation 1 derived from the relational expression relating to the target temperature is used as the minimum cooling time. This allows us to confirm that the battery, specifically the electrolyte of the battery, is cooled. In addition, when the battery is cooled for a time longer than the value of the formula 1, No fire occurs during the crushing process. Figures 8a and 8b show examples of the minimum cooling time of the present invention. 8c and 8d are photographs of comparative examples according to the minimum cooling time of the present invention.

[0070] Referring to Figures 8a and 8b, the minimum cooling time required to cool the battery is This experiment was conducted to determine the fire outbreak status of crushed materials when they were frozen for a period of time less than 10 minutes. In this experiment, the battery weight was 25 kg, the external cooling temperature was -95°C, and the target freezing temperature was -70°C. In the case of °C, when the value of the following formula 1 is 7 hours, the experiment is carried out for 5 hours, which is lower than the value of the formula 1. This is what happened.

[0071] <Expression 1> Minimum cooling time = A × (W 0.33 ) (A=4×e (-0.02×dT) , W = battery pack weight (kg), dT = | external cooling Temperature - target temperature ||| means absolute value.)

[0072] Referring to Figures 8c and 8d, the battery is frozen for more than the minimum freezing time required for cooling. The experiment was conducted to determine the fire outbreak state of the crushed material when the crushed material was The experiment was conducted with the same battery weight, external cooling temperature, and minimum freezing time of 7 hours or more. This is what happened.

[0073] Table 2 below shows the same battery weight, external cooling temperature, and minimum The fire outbreak state in the example and the comparative example in relation to the freezing time is compared. The state is judged as "O" if a fire is observed after the battery is crushed, and "O" if not. The combination was "X".

[0074] [Table 2]

[0075] Looking at Table 2, the battery is cooled at a value smaller than the value of Equation 1, which corresponds to the minimum cooling time. In this case, the electrolyte is not cooled, and it has been confirmed that a fire may occur after the battery is crushed. In this way, when the battery is cooled using the minimum cooling time as the value of Equation 1, It was confirmed that no fires occurred after crushing and that the crushed material could be used stably. The present invention is not limited to the above embodiments and may be manufactured in various different forms. A person having ordinary skill in the art to which the present invention pertains would be able to understand the technical concept of the present invention. It is understood that the invention may be embodied in other specific forms without changing the concept or essential characteristics. Therefore, the above-described embodiment is to be considered as illustrative in all respects. It should be understood as non-limiting.

Claims

1. A battery pack including a plurality of lithium-ion batteries as unit batteries is formed by satisfying the following formula 1. and cooling and freezing the product for a minimum cooling time or more. and crushing the frozen battery pack. <Formula 1> Minimum cooling time = A x (W ０．３３ ) (A = 4 × e （－０．０２×ｄＴ） , W = battery weight (kg), dT = | external cooling Temperature - target temperature |, || means absolute value.)

2. The freezing step is performed by cooling at a temperature between -150°C and -60°C. Item 1. The processing method according to item 1.

3. The freezing step is performed by cooling at −60° C. to −20° C., The crushing step may be performed using an inert gas, carbon dioxide, nitrogen, water, or a combination thereof.

2. The method of claim 1, wherein the method is carried out under conditions that provide a

4. The freezing step is performed by cooling at −60° C. to −20° C., The crushing step is carried out under a vacuum atmosphere of 100 torr or less. The processing method according to claim 1 .

5. The crushing step is carried out until the maximum size of the crushed product is 10 mm or less. The processing method according to claim 1 , wherein

6. After the crushing step, a magnetic separation step is performed to separate products having a maximum size of 1 mm or less.

2. The method of claim 1, further comprising the step of separating or gravity separating.

7. After the freezing step and before the crushing step, the frozen battery pack The method of claim 1 further comprising the step of crimping.

8. The crimping step is performed so that the thickness of the battery pack becomes half or less of the thickness before freezing. The method of claim 7, wherein the processing is carried out as follows.

9. A battery pack including a plurality of lithium-ion batteries as unit batteries is formed by satisfying the following formula 1. and crushing the battery pack while cooling and freezing the battery pack for a minimum cooling time or more. Including, battery treatment methods. <Formula 1> Minimum cooling time = A x (W ０．３３ ) (A = 4 × e （－０．０２×ｄＴ） , W = battery weight (kg), dT = | external cooling Temperature - target temperature |, || means absolute value.)

10. The freezing step is performed by cooling at a temperature between -150°C and -60°C. Item 10. The processing method according to Item 9.

11. The freezing step is performed by cooling at −60° C. to −20° C., The crushing step may be performed using an inert gas, carbon dioxide, nitrogen, water, or a combination thereof.

10. The method of claim 9, wherein the method is carried out under conditions that provide a

12. The freezing step is performed by cooling at −60° C. to −20° C., The crushing step is carried out under a vacuum atmosphere of 100 torr or less. The processing method according to claim 9.

13. The crushing step is carried out until the maximum size of the crushed product is 10 mm or less. The processing method according to claim 9, wherein

14. After the crushing step, a magnetic separation step is performed to separate products having a maximum size of 1 mm or less.

10. The method of claim 9, further comprising the step of separating or gravity separating.

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