JP6748274B2 - How to recover valuables from lithium-ion secondary batteries - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention can recover valuable materials from the positive electrode current collector, negative electrode current collector, positive electrode active material, etc. of lithium-ion secondary batteries that are discarded due to defective products generated during the manufacturing process and the life of the equipment and batteries used. To recover valuable resources from various lithium-ion secondary batteries.

Lithium-ion rechargeable batteries are lighter weight, higher capacity, higher electromotive force rechargeable batteries than conventional lead-acid batteries and NiCd rechargeable batteries, and are used as rechargeable batteries for personal computers, electric vehicles, portable devices, etc. Has been done. For example, in the positive electrode of a lithium ion secondary battery, valuable materials such as cobalt and nickel are lithium cobalt oxide (LiCoO ₂ ), a ternary positive electrode material (LiNi _x Co _y Mn _z O ₂ (x+y+z=1)), etc. Is used as.

Since the use of the lithium ion secondary battery is expected to continue expanding in the future, valuables will be discarded from the lithium ion secondary battery that is discarded due to defective products or equipment used during the manufacturing process and the life of the battery. Collection is desired from the viewpoint of resource recycling. When recovering a valuable material from a lithium ion secondary battery, it is important to separate and recover various metals used from the viewpoint of increasing the value of the recovered material.

As a method of recovering a valuable material from a lithium ion secondary battery, a method of recovering cobalt and nickel from a crushed material of a heat treated lithium ion battery has been proposed. For example, in Patent Document 1, by separating the aluminum of the positive electrode current collector from the cobalt/nickel derived from the positive electrode active material by adjusting the temperature during the heat treatment, the crushing/classification of copper/aluminum/iron A recovery method that enhances separation efficiency is disclosed. Further, Patent Document 2 discloses a recovery method including a melting and separating step of melting and separating an aluminum material, a crushing step of crushing a non-melted material, and a magnetic separation step of magnetically sorting crushed materials. ing. Further, Non-Patent Document 1 discloses a technique in which cobalt that is crushed after heating and concentrated under a sieve is subjected to magnetic separation or flotation to remove impurities and recover the cobalt.

JP 2012-79630 A Japanese Patent No. 6268130

Examination of heating conditions suitable for cobalt recovery from used lithium-ion battery by magnetic separation Chemical Engineering Papers, Vol. 43, No. 4, pp. 213-218, 2017

When the lithium ion secondary battery is heat-treated and then crushed and classified, iron and aluminum derived from the outer container and copper derived from the negative electrode current collector are recovered as coarse-grain products. Further, although cobalt/nickel is concentrated in the fine-grained product, some metal derived from the current collector is also mixed in the fine-grained product. For recycling cobalt/nickel, it is required to separate and collect the metal derived from the current collector and the negative electrode active material from the fine-grained product. In particular, copper and cobalt/nickel precipitate from the solution in the same pH range. It is difficult to remove the copper by causing precipitation by neutralization. Further, the negative electrode active material such as carbon is a particle of several tens of nm, and dry physical selection causes an adhesive force mainly due to crosslinking of water between cobalt/nickel-containing particles and carbon particles, which makes it difficult to remove carbon. Is. Further, the cobalt-nickel-containing particles recovered by dry physical screening contain several% of fluorine in the methods described in Patent Documents 1 and 2 described above, and a fluorine removal step is required. Reduce the quality of negative electrode current collector-derived metals such as copper in the cobalt/nickel concentrate to less than 0.2%, fluorine quality to less than 1%, and the quality of substances derived from negative electrode active materials such as carbon to less than 5%. Was difficult.

The present invention has been made in view of the above circumstances, and provides a means capable of recovering valuable materials such as cobalt and nickel with a low negative electrode collector-derived metal grade, a fluorine grade, and a substance grade derived from a negative electrode active material. With the goal.

In order to solve the above problems, according to the present invention, a heat treatment step of heat treating a lithium ion secondary battery, a crushing step of crushing the heat treated product obtained in the heat treatment step, and a crushing obtained in the crushing step The method includes a classification step of classifying a product into a coarse-grain product and a fine-grain product at a classification point of 0.45 mm or more, and a wet magnetic separation step of wet-magnetic separation of the fine-grain product obtained in the classification step. The heat treatment of the lithium ion secondary battery at 670° C. or more and 1100° C. or less, the magnetic substance obtained in the wet magnetic separation step has a fluorine quality of less than 1%, and the non-magnetic substance slurry obtained in the wet magnetic separation step is obtained. A method for recovering a valuable resource from a lithium ion secondary battery is provided, in which fluorine is recovered in the separated liquid by performing solid-liquid separation . The crushing step and the classification step can be performed simultaneously. For example, it may be carried out as a crushing/classifying step of classifying the crushed product into a coarse-grain product and a fine-grain product while crushing the heat-treated product obtained in the heat treatment process.

In this collecting method, a classification point of 0.6 to 2.4 mm may be used in the classification step. Further, aluminum may be melted and separated and recovered in the heat treatment step. The content of the substance derived from the negative electrode active material in the magnetic substance obtained in the wet magnetic separation step may be less than 5%. In that case, the substance derived from the negative electrode active material may be carbon. The magnetic substance obtained in the wet magnetic separation step may have a metal quality derived from the negative electrode current collector of less than 0.2%. In that case, the metal derived from the negative electrode current collector is, for example, copper. Further, the heat treatment step may be performed in a low oxygen atmosphere having an oxygen concentration of 10.5% by mass or less. Further, it may have a dry magnetic separation step in which the coarse-grained product obtained on the sieve in the classification step is subjected to dry magnetic separation. Further, carbon dioxide gas may be blown into the liquid after the solid-liquid separation of the non-magnetic substance slurry separated in the wet magnetic separation process.

When magnetically selecting the fine-grained product obtained in the classification step, when the dry-type magnetically-selected, the particles are aggregated due to the moisture adhered between the particles, and the negative electrode current collector-derived metal particles and the negative electrode containing 10% or more of the fine-grained product The active material particles and cobalt/nickel particles cannot be separated sufficiently. In addition, the dry method requires an additional step of removing fluorine in order to remove the fluorine in the cobalt-nickel concentrate magnetically recovered. In the present invention, wet magnetic selection is for the purpose of solving these problems. In the present invention, in the wet magnetic separation step, the negative electrode current collector-derived metal and the negative electrode active material are separated into a non-magnetic product slurry, and cobalt and nickel are recovered as a magnetic product. Fluorine and lithium are dissolved during slurrying of raw materials and wet magnetic separation, and are separated into a non-magnetic product slurry. By solid-liquid separating this non-magnetic substance slurry, the metal derived from the negative electrode current collector can be separated into a residue, and fluorine and lithium can be separated into a liquid. Further, the lithium hydroxide in the liquid can be recovered as lithium carbonate by blowing carbon dioxide gas. Although leaching treatment is required to recover lithium, in the present invention, in the wet magnetic separation step, water leaching of lithium, leaching of fluorine and removal of the negative electrode current collector-derived metal-cobalt-nickel can be performed simultaneously. The number of steps can be reduced.

According to the present invention, when recovering valuables from a lithium ion secondary battery, valuables such as cobalt and nickel can be recovered with a low metal/fluorine grade derived from the negative electrode current collector.

It is a flow chart for explaining the collection method concerning an embodiment of the invention.

Hereinafter, an example of a mode for carrying out the present invention will be described.

<Lithium-ion secondary battery>
A lithium-ion secondary battery is a secondary battery that performs charging or discharging by moving lithium ions between a positive electrode and a negative electrode, for example, a positive electrode, a negative electrode, a separator, an electrolyte containing an electrolyte and an organic solvent. Examples thereof include a liquid and an outer container that is a battery case that contains a positive electrode, a negative electrode, a separator, and an electrolytic solution.

The shape, structure, size, material, etc. of the lithium ion secondary battery are not particularly limited and can be appropriately selected according to the purpose. Examples of the shape of the lithium ion secondary battery include a laminate type, a cylinder type, a button type, a coin type, a square type, and a flat type.

The positive electrode is appropriately selected depending on the intended purpose without any limitation, provided that it has a positive electrode material on the positive electrode current collector. The shape of the positive electrode is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a flat plate shape and a sheet shape.

The shape, structure, size, material and the like of the positive electrode current collector are not particularly limited and can be appropriately selected according to the purpose. Examples of the shape of the positive electrode current collector include a foil shape. Examples of the material of the positive electrode current collector include stainless steel, nickel, aluminum, copper, titanium and tantalum. Of these, aluminum is preferable.

The positive electrode material is not particularly limited and may be appropriately selected depending on the purpose. For example, a positive electrode material containing at least a positive electrode active material containing a rare valuable substance, and optionally containing a conductive agent and a binder resin. And so on. The rare valuable is not particularly limited and may be appropriately selected depending on the purpose, but is preferably at least one of cobalt, nickel and manganese.

Examples of the positive electrode active material include lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), lithium manganate (LiMn ₂ O ₄ ), lithium cobalt nickel oxide (LiCo _1/2 Ni _1/2 O ₂ ). , LiNi _x Co _y Mn _z O ₂ and their composites.

The conductive agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include carbon black, graphite, carbon fiber, and metal carbide.

The binder resin is not particularly limited and may be appropriately selected depending on the intended purpose.For example, vinylidene fluoride, tetrafluoroethylene, acrylonitrile, a homopolymer or copolymer of ethylene oxide, styrene-butadiene rubber. And so on.

The negative electrode is appropriately selected depending on the intended purpose without any limitation, provided that it has a negative electrode material on the negative electrode current collector. The shape of the negative electrode is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a flat plate shape and a sheet shape.

The shape, structure, size, material and the like of the negative electrode current collector are not particularly limited and can be appropriately selected according to the purpose. Examples of the shape of the negative electrode current collector include a foil shape. Examples of the material of the negative electrode current collector include stainless steel, nickel, aluminum, copper, titanium and tantalum. Of these, copper is preferable.

The negative electrode material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include carbon materials such as graphite and hard carbon, titanate, silicon, and composites thereof.

Note that the positive electrode current collector and the negative electrode current collector have a structure of a stacked body, and the stacked body is not particularly limited and can be appropriately selected depending on the purpose.

In the embodiment of the present invention, various valuable materials such as aluminum, cobalt, nickel, and copper contained in the lithium ion secondary battery are efficiently separated and recovered by the procedure shown in FIG. The lithium ion secondary battery used for recovery is not particularly limited and may be appropriately selected depending on the purpose, for example, a defective lithium ion secondary battery generated in the manufacturing process of the lithium ion secondary battery, Examples thereof include a lithium ion secondary battery that is discarded due to a defective used device or the life of the used device, and a used lithium ion secondary battery that is discarded due to its life.

<Heat treatment process>
As shown in FIG. 1, first, a heat treatment step (heat treatment) is performed on a lithium ion secondary battery (LIB). The heat treatment temperature is not particularly limited as long as it is a temperature equal to or higher than the melting point of the low melting point current collector of the positive electrode current collector and the negative electrode current collector and lower than the melting point of the high melting point current collector, and depending on the purpose. The temperature is preferably 670°C or higher, more preferably 670°C or higher and 1100°C or lower, and particularly preferably 700°C or higher and 900°C or lower. If the heat treatment temperature is lower than 670° C., the current collector having a low melting point may not be sufficiently embrittled, and if it exceeds 1100° C., a current collector having a low melting point, a current collector having a high melting point, and Any of the outer containers becomes brittle, and the efficiency of separating the current collector and the outer container by crushing and classification is reduced. Further, when the outer container of the lithium ion secondary battery is melted during the heat treatment, by placing a tray for collecting the molten metal under the lithium ion secondary battery, a metal and an electrode derived from the outer container are placed. The parts can be easily separated.

By performing heat treatment at a predetermined heat treatment temperature, for example, in a laminate in which the positive electrode current collector is aluminum and the negative electrode current collector is copper, the positive electrode current collector made of aluminum foil becomes brittle, and the crushing step described below It becomes easy to make fine particles. The embrittlement of the positive electrode current collector occurs due to melting or oxidation reaction. Further, the aluminum that has melted and flowed down is collected in a saucer. On the other hand, since the negative electrode current collector made of copper is heat-treated at a temperature lower than the melting point of copper, it does not melt and can be highly sorted in the later-described dry magnetic separation step. In addition, when either the laminate or the lithium ion secondary battery is housed in an oxygen-shielding container and subjected to heat treatment, the positive electrode current collector made of aluminum foil is melted and embrittled, and is easily atomized in a crushing step described later. On the other hand, the negative electrode current collector made of copper has a low oxygen partial pressure due to the oxygen shielding effect of the oxygen shielding container and the reduction effect of the negative electrode active material such as carbon contained in the laminate or the lithium ion secondary battery. Since it is heat treated in, no embrittlement due to oxidation does occur. Therefore, by the crushing in the crushing step, the positive electrode current collector is finely crushed, and the negative electrode current collector remains as coarse particles even after the crushing, which makes it possible to select more effectively and highly in the classification step described later. ..

The heat treatment time is appropriately selected depending on the intended purpose without any limitation, but it is preferably 1 minute or more and 5 hours or less, more preferably 1 minute or more and 2 hours or less, and particularly preferably 1 minute or more and 1 hour or less. .. The heat treatment time may be any heat treatment time required for the current collector having a low melting point to reach a desired temperature, and the holding time may be short. When the heat treatment time is within a particularly preferable range, it is advantageous in terms of cost required for the heat treatment.

The heat treatment method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a heat treatment furnace. Examples of the heat treatment furnace include a rotary kiln, a fluidized bed furnace, a tunnel furnace, a batch furnace such as a muffle, a cupola, and a stalker furnace.

The atmosphere used for the heat treatment is not particularly limited and may be appropriately selected depending on the intended purpose, but may be performed in the air. The atmosphere having a low oxygen concentration is preferable because the metal derived from the positive electrode current collector and the metal derived from the negative electrode current collector can be recovered with high quality and high recovery rate.

As a method of realizing the above low oxygen atmosphere, the lithium ion secondary battery or the laminated body may be housed in an oxygen shielding container and heat treated. The material of the oxygen shielding container is not particularly limited as long as it is a material that does not melt at the heat treatment temperature described above, and can be appropriately selected according to the purpose, and examples thereof include iron and stainless steel. An opening is preferably provided in the oxygen shielding container in order to release the gas pressure due to the combustion of the electrolytic solution in the lithium ion battery or the laminate. The opening area of the opening is preferably 12.5% or less of the surface area of the exterior container in which the opening is provided. The opening area of the opening is more preferably 6.3% or less with respect to the surface area of the exterior container in which the opening is provided. If the opening area of the opening exceeds 12.5% of the surface area of the outer container, most of the current collector is likely to be oxidized by the heat treatment. The shape, size, formation location, etc. of the opening are not particularly limited and can be appropriately selected according to the purpose.

<Crushing process>
Next, a crushing step of crushing the heat-treated product (LIB heat-treated product) obtained in the heat-treatment process is performed. In the crushing step, the heat-treated product is preferably crushed by impact to obtain a crushed product.

The crushing is not particularly limited and can be appropriately selected according to the purpose. Examples of the method of crushing by impact include a method of throwing with a rotating striking plate and striking a collision plate to give an impact, and a method of striking a heat-treated product with a rotating striking element (beater). For example, a hammer crusher or a chain. It can be done by a crusher or the like. In addition, a method of hitting the heat-treated product with balls or rods of ceramic or iron can be used, and it can be performed with a ball mill or a rod mill. Further, it can be carried out by crushing with a biaxial crusher having a short blade width and a short blade crossing for crushing by compression.

By crushing to obtain a crushed product, the crushing of the active material and the current collector with a low melting point is promoted, while the current collector with a high melting point whose morphology is not significantly changed is present in the form of a foil. .. Therefore, in the crushing step, the high melting point current collector is only cut, and the fine melting of the high melting point current collector is less likely to proceed as compared with the low melting point current collector, so the classification step described later In (1), a crushed product can be obtained in which the current collector having a low melting point and the current collector having a high melting point can be efficiently separated.

The crushing time is not particularly limited and may be appropriately selected depending on the intended purpose, but the treatment time per 1 kg of the lithium ion secondary battery is preferably 1 second or more and 30 minutes or less, and more preferably 2 seconds or more and 10 minutes or less. It is preferably 3 seconds or more and 5 minutes or less. If the crushing time is less than 1 second, it may not be crushed, and if it exceeds 30 minutes, it may be excessively crushed.

<Classification process>
Next, a classification step of classifying the crushed material obtained in the crushing step into a coarse grain product and a fine grain product is performed. The classification method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a vibrating screen, a multi-stage vibrating screen, a cyclone, a JIS Z8801 standard screen, a wet vibration table, an air table, etc. may be used. be able to.

The classification point used in the classification step can be appropriately selected according to the purpose as long as it is 0.45 mm or more. For example, it is desirable to use a classification point of 0.6 to 2.4 mm. If the classification point exceeds 2.4 mm, the metal from the outer container or the one with a higher melting point may be more mixed into the fine-grain product, and the separation performance from the cobalt/nickel derived from the active material may decrease. On the other hand, when the classification point is less than 0.6 mm, the metal derived from the collector having a low melting point and the mixing of the active material into the coarse-grained product increase, and the metal derived from the collector having a high melting point in the coarse-grained product increases. In some cases, the quality of the product is deteriorated, and the recovery rate of cobalt-nickel derived from the active material in the fine grain product is less than 60%. Also, when using a sieve as a classification method, a crushing accelerator, for example, by placing stainless balls or alumina balls on the sieve and sieving, a small crushed material adhering to a large crushed material is converted into a large crushed material. By separating from the above, it is possible to efficiently separate the large crushed material and the small crushed material. As a result, the quality of the recovered metal can be further improved. The crushing step and the classification step can be performed simultaneously. For example, it may be performed as a crushing/classifying step (crushing/classifying) of classifying the crushed material into a coarse-grained product and a fine-grained product while crushing the heat-treated material obtained in the heat treatment step.

By this classification, the metal derived from the outer container and the collector having a high melting point can be recovered as a coarse particle product, and the cobalt-nickel-lithium derived from the active material can be recovered as a fine particle product. The fine-grained product may be classified again. By removing fine particles of, for example, 150 μm or less from the fine particles by this classification again, it is possible to reduce the negative electrode active material content contained in the non-magnetically adsorbed material in the wet magnetic separation.

<Dry magnetic separation process>
Next, a dry magnetic separation step can be performed on the coarse-grained product obtained in the classification step. Iron is recovered as a magnetic substance, and a negative electrode current collector-derived metal such as copper is recovered as a non-magnetic substance.

<Wet magnetic separation process>
On the other hand, the fine granule product obtained in the classification step is subjected to a wet magnetic separation step (wet magnetic separation) to recover cobalt and nickel as magnetic substances. As described above, when magnetically sorting the fine-grained product obtained in the classification step, when dry-type magnetically-selected, agglomeration of the particles occurs due to the adhered moisture between the particles, and the negative electrode current collector-derived metal particles and fine particles It is not possible to sufficiently separate the negative electrode active material fine particles and the cobalt/nickel particles containing 10% or more in the product. In the present invention, in the wet magnetic separation step, the material derived from the negative electrode active material and the metal derived from the negative electrode current collector are separated into a non- magnetically adsorbed slurry , and cobalt and nickel are recovered in the magnetically adsorbed material.
In this magnetic substance, for example, the carbon derived from the negative electrode active material contained in the magnetic substance can be less than 5%. Further, the negative electrode current collector-derived metal (typically copper) contained in the magnetic substance can be less than 0.2%.

On the other hand, lithium is dissolved in the liquid during the slurrying of the raw material and the wet magnetic separation, and is separated into a non-magnetized material slurry . By solid-liquid separating the non-magnetic substance slurry, the negative electrode current collector-derived metal and the negative electrode active material can be separated into residues. Further, carbon dioxide gas is blown into the liquid separated by the solid-liquid separation to precipitate as lithium carbonate, and lithium is recovered. Before the carbon dioxide gas is blown in, a pretreatment step such as an impurity removal step or a liquid concentration step for the purpose of increasing the lithium concentration may be included. On the other hand, for example, fluorine is recovered in the remaining liquid. Therefore, the fluorine quality in the magnetic substance can be less than 1%. In order to recover lithium and separate fluorine from cobalt/nickel, a leaching treatment is necessary. In the present invention, however, in the wet magnetic separation step, water leaching of lithium and leaching of fluorine and removal of a negative electrode current collector-derived metal-cobalt. Since nickel can be separated at the same time, the number of steps can be reduced.

Examples of the present invention will be described below. The present invention is not limited to the examples below.

As shown in the flow chart of FIG. 1, using a muffle furnace (FJ-41, Yamato Scientific Co., Ltd.) as a heat treatment device, a lithium ion secondary battery of about 3.7 kg was subjected to a heat treatment temperature of 850° C. (Hold), and the heat treatment process was performed under the condition that the air supply rate was 5 L/min. Next, in the crushing step, a hammer crusher (Makino-type swing hammer crusher HC-20-3.7, manufactured by Makino Sangyo Co., Ltd.) was used as a crushing device, 50 HZ (hammer peripheral speed 38 m/s), and punching metal at the exit portion. Was additionally crushed once under the condition of the hole diameter of 10 mm.

In the classification step, a crushed material obtained in the crushing step was sieved using a sieve having a mesh size of 1.2 mm (diameter 200 mm, manufactured by Tokyo Screen Co., Ltd.). After sieving, a 1.2 mm sieve (coarse particles) and a sieve (fine particles) of 1.2 mm were collected.

The fine granules obtained were subjected to wet magnetic separation using a drum type magnetic separator at a magnetic force of 1500 G, a drum rotation speed of 45 rpm, a solid-liquid ratio of 10%, and a slurry supply rate of 100 ml/min to obtain a magnetic substance and a non-magnetic substance. The slurry was collected. The slurry of this non-magnetic substance was subjected to solid-liquid separation, and after the solid content was separated, carbon dioxide gas was blown into the solution to precipitate lithium carbonate.

On the other hand, for the coarse-grained product, dry magnetic separation was performed using a hand magnet under the conditions of a magnetic force of 1500 G and a distance of the hand magnet from the coarse-grained product of 10 mm to collect a magnetic substance and a non-magnetic substance.

After measuring the mass of the magnetic and non-magnetic substances obtained for each of the coarse-grain product and the fine-grain product, the mixture was heated and dissolved in aqua regia, and the high-frequency inductively coupled plasma optical emission spectrometer (iCaP6300, Thermo Fisher Scientific Co., Ltd.) was used. Manufactured) to determine the recovery rate of cobalt and nickel and the content ratio of various metals recovered. The grade of each product is shown in Table 1, and the recovery rate of each valuable substance to each product is shown in Table 2. In addition, Table 1 shows the content (feed) of each element in the raw material (lithium ion secondary battery). In Tables 1 and 2, (%) is% by mass. In addition, the upper part (coarse particles) is shown by "+" and the lower part (fine particles) is shown by "-".

The same procedure as in Example 1 was carried out except that the sieve opening in Example 1 was set to 2.4 mm. The grade of each product is shown in Table 1, and the recovery rate of each valuable substance to each product is shown in Table 2.

The same procedure as in Example 1 was performed except that the sieving aperture in Example 1 was set to 4.8 mm. The grade of each product is shown in Table 1, and the recovery rate of each valuable substance to each product is shown in Table 2.

The same procedure as in Example 1 was carried out except that the sieve opening in Example 1 was changed to 0.6 mm. The grade of each product is shown in Table 1, and the recovery rate of each valuable substance to each product is shown in Table 2.

(Comparative Example 1)
The same procedure as in Example 1 was performed except that the sieving mesh size in Example 1 was 0.3 mm. Table 1 shows the grade of each product (how many% each element occupies in the product), and the recovery rate of each valuable substance to each product (how much each element was recovered in the product). Are shown in Table 2, respectively.

(Comparative example 2)
The same procedure as in Example 1 was carried out except that the magnetic separation of fine particles in Example 1 was changed to the dry type. The grade of each product is shown in Table 1, and the recovery rate of each valuable substance to each product is shown in Table 2.

In Example 1, as shown in Table 2, 90% or more of cobalt and nickel could be recovered as a magnetic substance. Further, as shown in Table 1, regarding the grade of cobalt/nickel, the grade of cobalt/nickel is 80% or more in total, the grade of copper, which is a metal derived from the negative electrode current collector, is less than 0.2%, and the grade of fluorine is less than 1%. The quality of carbon, which is an element derived from the negative electrode active material, was less than 5%, and high quality cobalt/nickel could be recovered.
In Example 2, as in Example 1, high-quality cobalt-nickel having a total cobalt/nickel grade of 80% or more, a copper grade of less than 0.2%, a fluorine grade of less than 1%, and a carbon grade of less than 5% was used. 90% or more could be recovered.
In Example 3, as in Example 1, 90% or more of high-quality cobalt nickel having a carbon quality of less than 5% could be recovered. However, iron was mixed in the 37% fine grain product, and 35% was recovered in the magnetic substance (=Co/Ni concentrate) by magnetic separation of the fine grain product. As a result, as shown in Table 1, the iron grade in the magnetic substance was about 13%.
In Example 4, 85% or more of high-quality cobalt/nickel having a total cobalt/nickel grade of 80% or more, a copper grade of less than 0.2%, a fluorine grade of less than 1%, and a carbon grade of less than 5% could be recovered.

In Comparative Example 1, as shown in Table 2, 48% and 53% of cobalt and nickel were recovered in the coarse particles, and they could not be separated and recovered from other constituents.
In Comparative Example 2, as shown in Table 2, 41% of carbon was recovered in the magnetic substance, and as a result, as shown in Table 1, the carbon quality in the magnetic substance was about 15%. Moreover, the fluorine grade was 1% or more.

Claims (9)

A heat treatment step of heat treating the lithium ion secondary battery,
A crushing step of crushing the heat-treated product obtained in the heat-treating step,
A classifying step of classifying the crushed material obtained in the crushing step into a coarse-grain product and a fine-grain product at a classification point of 0.45 mm or more;
A wet magnetic separation step of wet magnetic separation of the fine grain product obtained in the classification step,
In the heat treatment step, the lithium ion secondary battery is heat treated at 670° C. or higher and 1100° C. or lower ,
The magnetic substance obtained in the wet magnetic separation step has a fluorine quality of less than 1%,
A method of recovering a valuable resource from a lithium ion secondary battery, characterized in that solid-liquid separation is performed on the non-magnetically adsorbed slurry obtained in the wet magnetic separation step to recover fluorine in the separated liquid . The method for recovering a valuable resource from a lithium ion secondary battery according to claim 1, wherein a classification point of 0.6 to 2.4 mm is used in the classification step. The method for recovering a valuable resource from a lithium ion secondary battery according to claim 1, wherein aluminum is melted and separated in the heat treatment step to be recovered. The lithium ion secondary according to any one of claims 1 to 3, wherein the magnetic substance obtained in the wet magnetic separation step has a content of a substance derived from a negative electrode active material of less than 5%. How to recover valuables from batteries. The method of recovering a valuable resource from a lithium ion secondary battery according to claim 4, wherein the substance derived from the negative electrode active material is carbon. The lithium ion ion according to any one of claims 1 to 5, wherein the magnetic substance obtained in the wet magnetic separation step has a metal quality derived from a negative electrode current collector of less than 0.2%. How to recover valuables from the next battery. The method for recovering a valuable resource from a lithium-ion secondary battery according to claim 6, wherein the metal derived from the negative electrode current collector is copper. Said heat treatment step, the oxygen concentration and performing in a low oxygen atmosphere at less 10.5 wt%, of the valuable materials from lithium-ion secondary battery according to any one of claims 1 to 7 Recovery method. The wet magnetic separation after the step solid-liquid separation, non-magnetically attracted material slurry separation, and wherein the blowing carbon dioxide gas into the liquid, a lithium ion secondary battery according to any one of claims 1 to 8 To collect valuables from.