KR102096341B1 - Method for recovering base materials from waste battery - Google Patents

Abstract

The present invention relates to a method for recovering raw materials from a waste cell, more specifically, (a) calcining the waste cell, (b) crushing the calcined waste cell, and (c) crushing the crushed waste. Separating the active material by screening with a screen sorter, (d) pulverizing the crushed material from which the active material is separated, and (e) separating the crushed crushed material into copper, aluminum, and a separator, respectively, using specific gravity difference It characterized in that it comprises a step. According to the method for recovering the raw material from the waste battery according to the present invention, aluminum (Al), copper (Cu), separator, active material graphite (C), cobalt (Co), nickel (Ni) from the discarded waste battery without environmental burden , Manganese (Mn) and the like, each has the advantage of being separately collected and recycled. In addition, there is an advantage that the separation and recovery costs can be lowered.

Description

METHOD FOR RECOVERING BASE MATERIALS FROM WASTE BATTERY

The present invention relates to a method for recovering a raw material from a waste cell, and more particularly, to a method for efficiently separating and recovering the raw materials contained in the crushed material according to its characteristics after heat treatment and crushing the waste cell.

The primary battery is an irreversible battery that cannot be recharged, but the secondary battery is a battery that can be recharged by reversible oxidation and reduction reactions.

The secondary battery contains graphite, cobalt, nickel, or manganese, which are electrically active materials, and copper and aluminum, which are electrode materials, so it is a great waste to leave the secondary battery that has reached its end of life.

2. Description of the Related Art As the use of secondary batteries has recently increased, the amount of secondary batteries has been rapidly increased, and the technology of recovering the valuable metals therefrom has become more important in terms of resource saving and environmental conservation.

Currently, a generally known secondary battery treatment method is a process in which a battery is dismantled to recover cobalt, and a waste cell is crushed to remove iron components by magnetic force lines, and an acid leaching process targets a crushed product in which cobalt components are concentrated. It consists of a process of recovering cobalt through a precipitation method, an electrowinning method, and a solvent extraction method. This process can be divided into two steps: physical separation method and wet concentration method. Due to the complicated process during physical separation, there is a high possibility of loss of cobalt (Co), and the wet concentration process is generally a low-temperature process, which is advantageous for high purity. On the other hand, mass processing is difficult and slow reaction rate is pointed out as a disadvantage.

In order to solve these shortcomings, Korean Patent Registration No. 10-0717389 proposed a method of recovering valuable metals such as cobalt and lithium by using a high-temperature firing method.

In addition, Korean Patent Registration No. 10-0637680 proposes a method of crushing a secondary battery, firing to form a mass of agglomerates, and then pulverizing, sorting and classifying it to obtain cobalt in powder form.

Also, in Korean Patent Registration No. 10-1368216, cobalt (Co) is recovered through a reduction reaction of lithium cobalt oxide (LiCoO ₂ ), a positive electrode active material of a secondary battery, and then lithium oxide (Li ₂ O) produced through the above process is recovered. ) Has been proposed to recover lithium (Li) by electrolysis in lithium chloride, a molten salt.

However, all of these pre-registered patents have the disadvantage of not only separating and recovering expensive cobalt and lithium, but not separating and recovering copper, aluminum used as an electrode, and synthetic resin used as a separator, as well as other active materials. In addition, there was no economic advantage due to the increase in separation and recovery costs.

KR 10-0717389 B1 KR 10-0637680 B1 KR 10-1368216 B1

Therefore, the object of the present invention is to solve the various problems of the conventional waste battery treatment method, the environmental burden of raw materials such as aluminum (Al), copper (Cu), separator, active material contained in the waste battery It is to provide a method that can be separated and recovered simply and efficiently.

The method for recovering a raw material from a waste battery according to the present invention for achieving the above object includes: (a) calcining a waste battery, (b) crushing the calcined waste battery, and (c) the crushing. Separating the active material by screening the crushed material with a screen sorter, (d) crushing the crushed material from which the active material is separated, and (e) using the specific gravity difference between the pulverized material to copper, aluminum and a separator. It characterized in that it comprises a step of separating each.

The active material is characterized in that it contains at least one of manganese (Mn), cobalt (Co), manganese (Mn), and graphite (C).

The step (a) is characterized in that it is fired at 400 to 600 ° C. for 90 to 180 minutes.

The step (b) is characterized in that it is crushed for 10 to 30 minutes at 1,000 to 2,000 rpm.

The step (e) is characterized in that it comprises the step of separating the copper from the pulverized pulverized material using an air separator, and separating the pulverized copper-separated material into aluminum and a separator using a sedimentation tank. do.

According to the method for recovering the raw material from the waste battery according to the present invention, aluminum (Al), copper (Cu), separator, active material graphite (C), cobalt (Co), nickel (Ni) from the discarded waste battery without environmental burden , Manganese (Mn) and the like, each has the advantage of being separately collected and recycled. In addition, there is an advantage that the separation and recovery costs can be lowered.

1 is a flow chart for a method for recovering raw materials from a waste battery according to the present invention.

Hereinafter, the present invention will be described in detail.

Before describing the present invention in detail, the waste battery described below may be a secondary battery, and it is revealed that the case surrounding the battery is removed.

That is, the secondary battery, aluminum sheet (Al sheet), copper sheet (Cu sheet), the separator and graphite (C), manganese (Mn), cobalt (Co) and nickel (Ni) attached to each of the sheets It consists of a powdery active material containing one or more. In addition, when manufacturing the secondary battery, the powders are adhered to each sheet with an organic material as an adhesive. In addition, it is natural that other active materials may be further included according to the type of the secondary battery, but this is not limited.

The present invention provides a simple and efficient method for separating graphite, manganese, cobalt, and nickel, as well as aluminum, copper, separator, graphite, and the like, contained in the waste battery. In particular, the present invention is characterized in that it is possible to increase the recovery efficiency of each raw material while separating and recovering the raw materials of the waste battery by type in a simple manner without environmental burden.

The method for recovering the raw material from the waste battery of the present invention includes: (a) calcining the waste cell, (b) crushing the calcined waste cell, and (c) screening the crushed crushed material with a screen sorter. Separating the active material, (d) crushing the crushed material from which the active material is separated, and (e) separating copper, aluminum and the separator using a specific gravity difference from the crushed crushed material. Is done.

In addition, the step (e) comprises the step of separating the copper from the pulverized pulverized material using an air separator, and separating the pulverized copper-separated material into aluminum and a separator using a sedimentation tank. It is characterized by.

Hereinafter, a method of recovering a raw material from a waste battery according to the present invention will be described in more detail step by step with reference to FIG. 1.

(a) The step of firing a waste cell.

First, an organic substance is volatilized by firing a waste battery in a firing furnace.

At this time, it is preferable that the firing is performed for 90 to 180 minutes in a firing furnace at 400 to 600 ° C. The firing temperature is less than 400 ° C, and organic materials such as adhesives in the waste cell are not volatilized and removed, so copper on the sheet and This is because the active material is not easily separated from the aluminum, and thus the effective separation of the active material is not achieved in a later process, and when it exceeds 600 ° C, aluminum or the like having a low melting point is melted, which makes the separation of the active material difficult, and the economic efficiency is also poor. In addition, it is because limiting the firing time is also not economically desirable if it is outside the above range.

In the present invention, the reason for firing the waste battery is to volatilize and remove organic substances such as adhesives and moisture contained in the waste battery through firing, so as to recover high-purity raw materials from which impurities have been removed, as well as in the following crushing step. This is to enable the active material from which the organic material adhesive is removed to be easily separated into a powder form from the separator, aluminum sheet, and copper sheet.

(B) crushing the calcined waste battery.

Next, the calcined waste battery is crushed.

When the sintered waste battery is crushed, the active material used as a powder raw material is separated from aluminum, copper, and a separator on the sheet into fine powders of several micrometers to tens of micrometers by crushing. In addition, the separator used for the sheet, copper and aluminum are crushed to a particle size of 100 µm or more.

This is because when the secondary battery is manufactured, the active material adheres fine powder within a few tens of micrometers to aluminum or copper, which is an electrode material on the sheet, using an organic material adhesive. This is because it is separated into fine powders within tens of micrometers by external force. That is, powders such as graphite (C), manganese (Mn), cobalt (Co), and nickel (Ni) used as the active material through the crushing process have a particle size of less than 100 μm, and are used as a sheet. Copper, aluminum, separators, etc., have a particle size of 100 µm or more.

To this end, the crushing is preferably performed for 10 to 30 minutes at a speed of 1,000 to 2,000 rpm. If it is outside this range, copper, aluminum, separators, etc., due to excessive crushing, have a particle size of less than 100 μm, and thus, It can be difficult to separate.

(c) the shredded Shredded  Separating the active material by screen screening

Next, by separating the crushed crushed material with a screen sorter, the active material on the powder is separated.

The screen sorter refers to a conventional vibration sorter, through which the powdery active material separated to a size of less than 100 μm can be separated into a crushed material including the aluminum, copper, and a separator.

Here, as described above, the separated powdery active material includes at least one of graphite (C), manganese (Mn), cobalt (Co), and nickel (Ni).

The screen sorter used in this step is a device well known in the art, and detailed description thereof is omitted, and it is natural to use a screen capable of sorting particles having a size of less than 100 μm and a size of 100 μm or more.

In addition, the crushed material from which the active material is separated may be additionally subjected to a washing and drying process, because the purity of the aluminum and copper and separation membranes may be additionally removed through washing and drying. to be.

(d) the active material is separated Shredded  Step of crushing.

Next, the crushed material from which the active material is separated, that is, a mixture of aluminum, copper, and a separator is pulverized. At this time, the size of the particles is not limited.

The reason for further including the crushing step in the present invention is to separate it by using a specific gravity difference in a post-process, because if the particle size is further reduced by further including a crushing step, more efficient separation is possible by specific gravity difference. to be.

(e) the crushed Crushed Specific gravity difference  Using copper, aluminum and separation steps, respectively.

Next, the pulverized pulverized product is separated into copper, aluminum, and a separator using a specific gravity difference. The specific gravity of the copper is 8.9 to 9, the specific gravity of aluminum is about 2.56, and the specific gravity of the separator, which is a synthetic resin, is less than 1, so if the specific gravity difference is used, these raw materials can be easily separated.

Specifically, first, copper is separated from the pulverized material using an air type separator. The pneumatic sorting machine is a device for sorting by a specific gravity difference of materials using the blowing of air. When the pulverized pulverized material is introduced into the pneumatic sorting machine and the air is blown, the small specific gravity aluminum and the separator fly away, Copper having a large specific gravity is not used to fly away and uses the principle of falling. Here, as the sorter, other wet sorters and dry sorters other than the air sorter may be used, but the implementation is not limited, but it is most preferable to use the air sorter when considering economics, efficiency, and the like.

Then, the pulverized product from which copper has been separated is introduced into a sedimentation tank to separate aluminum from the separator by a specific gravity difference. As described above, since the specific gravity of the aluminum is greater than 1 and the specific gravity of the separator is less than 1, when the precipitation tank is used, the aluminum with a large specific gravity sinks to the bottom of the precipitation tank, and the separator with a small specific gravity is in water. Will float.

Illustratively, the sedimentation tank is a canister with an open top, and a center of the bottom is formed in a funnel shape so that sediment can be collected. A water inlet and a raw material inlet are mounted on one side of the top of the barrel, and on the other side of the top of the barrel. A discharge outlet for discharging water is provided, and a transfer pipe and a motor for collecting the precipitate are provided at the bottom of the precipitation tank to be configured to recover the precipitate. Therefore, when water and copper separated pulverized material are introduced into the sedimentation tank through the water inlet and the raw material inlet, copper is precipitated on the bottom formed in a funnel shape, and the separator is discharged together with water through the outlet on the other side. In addition, the copper deposited on the bottom is recovered by the transfer pipe and the motor. In addition, the separator discharged together with water is removed through centrifugation, and the separator from which water is removed can be recycled through a drying process.

In addition, the separated copper and aluminum can be easily recycled after washing and drying, respectively.

According to the method of recovering the raw material from the waste battery as described above, the active material, as well as copper, aluminum and separation membrane can be efficiently separated and recovered from the waste battery, there is no environmental burden, and the recovery cost can also be reduced. have.

On the other hand, after the step (e) described above may further include the step of secondary firing the separated aluminum (Al) and copper (Cu).

This is because when the separated aluminum (Al) and copper (Cu) are fired, the purity of aluminum and copper can be further increased.

At this time, the firing may be performed for 1 to 3 hours at a temperature of 300 to 1,000 ° C, but this is not necessarily limited.

In addition, graphite (C), cobalt (Co), manganese (Mn), and nickel (Ni), which are the active materials separated in step (c), are separated by graphite through specific gravity difference, and then cobalt, manganese through leaching. , It is possible to separate each of the nickel, the technique for separating it is sufficient to follow the conventionally published method.

Using the above method, aluminum (Al), copper (Cu), separation membrane and active materials such as graphite (C), cobalt (Co), nickel (Ni), and manganese (Mn) are separated from the discarded waste battery, respectively. And by using a method of separating using a specific gravity difference by crushing and recycling, it has the advantage of being able to lower the recovery cost, thereby lowering the economical and environmental burden.

As described above, the present invention has been described in detail using preferred embodiments, but the scope of the present invention is not limited to specific embodiments, and should be interpreted by the appended claims. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

Claims (5)

delete delete delete delete (a) calcining the waste cell at 400-600 ° C. for 90-180 minutes,
(b) crushing the calcined waste battery at 1,000 to 2,000 rpm for 10 to 30 minutes,
(C) separating the active material by screening the crushed crushed material with a screen selector,
(D) crushing the crushed material is separated from the active material,
(e) separating the pulverized pulverized material into copper, aluminum, and a separator using a specific gravity difference, separating copper from the pulverized pulverized material using an air sorter, and pulverizing the copper-separated material. Separating into aluminum and a separator using a sedimentation tank,
(f) after the above step (e), a second calcination of the separated aluminum (Al) and copper (Cu) at a temperature of 300 to 1,000 ° C. for 1 to 3 hours;
The active material,
A method for recovering raw materials from a waste cell comprising one or more of manganese (Mn), cobalt (Co), manganese (Mn), and graphite (C).

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