JP2018028150A - Method for bleeding lithium ion battery scrap and method for recovering valuable metal - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for bleeding a lithium ion battery scrap and a method for recovering valuable metal capable of shortening bleeding time of the lithium ion battery scrap and thereby enhancing efficiency of a treatment of the lithium ion battery scrap in the case of deposition of the manganese when bleeding the lithium ion battery scrap.SOLUTION: There is provided a method for bleeding a lithium ion battery scrap containing at least a target metal by an acidic solution and a manganese ion and manganese dioxide exist at the same time by adding the manganese dioxide to an acidic solution with a condition that the manganese ion exists in the acidic solution. Or manganese ion and the manganese dioxide exist at the same time by adding the manganese dioxide to the acidic solution with a condition that no manganese ion exist in the acidic solution and then generating the manganese ion in the acidic solution.SELECTED DRAWING: Figure 1

Description

  TECHNICAL FIELD The present invention relates to a method for leaching lithium ion battery scrap and a method for recovering valuable metals, and in particular, to reduce the time required for leaching a target metal contained in lithium ion battery scrap, The present invention proposes a technology that can contribute to improving the processing efficiency of scrap.

Lithium ion batteries used in many industrial fields, including various electronic devices, use lithium metal salts containing manganese, nickel, and cobalt as cathode materials, and in recent years, the amount of use has increased. With the expansion of the range of use, the amount discarded due to the product life of the battery and defects in the manufacturing process is increasing.
Under such circumstances, it is desirable to easily recover the above-described expensive elements such as nickel and cobalt from lithium ion battery scraps that are discarded in large quantities at a relatively low cost for reuse.

In order to process lithium ion battery scrap for recovering valuable metals, first, for example, powdery or granular lithium ion battery scrap obtained through various processes such as roasting, crushing and sieving as required. Is leached with aqueous hydrogen peroxide, and lithium, nickel, cobalt, manganese, iron, copper, aluminum, and the like that can be contained therein are dissolved in the solution to obtain a solution after leaching.
Next, a solvent extraction method is performed on the leached solution to sequentially separate each metal element. Here, each valuable metal can be recovered by first recovering iron and aluminum, subsequently recovering manganese and copper, then cobalt, then nickel, and finally leaving lithium in the aqueous phase.

  As methods for recovering valuable metals from a secondary battery such as a lithium ion battery, Patent Documents 1 and 2 disclose “a valuable metal recovery method from a Co, Ni, Mn-containing lithium battery case” and “waste secondary battery”, respectively. "A method for recovering metal from a battery" is disclosed.

JP 2009-193778 A JP 2005-149889 A

  By the way, in the processing method of lithium ion battery scrap or the valuable metal recovery method as described in Patent Documents 1 and 2, the metal to be leached such as nickel and cobalt contained in the lithium ion battery scrap is acid leached. Here, metals such as manganese other than the target metal are also leached out. In this case, man-hours for extracting metals such as manganese contained in the solution after leaching are increased and the cost is increased, and depending on the form of the metal recovered after the solvent extraction, it cannot be reused as it is. There is a problem that further processing is required.

  In contrast, the inventor has found that when lithium ion battery scrap is leached, lithium, cobalt, and nickel are leached, while manganese is once leached and then precipitated as manganese dioxide. When manganese is precipitated as manganese dioxide in this way, manganese in the liquid after leaching can be reduced or removed in advance by separating the manganese dioxide from the liquid after leaching by solid-liquid separation or the like. The cost required for solvent extraction of manganese can be reduced.

  However, when separating and recovering manganese when leaching lithium ion battery scrap in this manner, it takes a relatively long time to deposit manganese as manganese dioxide. Forced to decline.

  An object of the present invention is to solve such problems of the prior art. The object of the present invention is to provide lithium ions when manganese is deposited when leaching lithium ion battery scraps. An object of the present invention is to provide a method for leaching lithium ion battery scrap and a method for recovering valuable metals that can shorten the leaching time of the battery scrap and thereby improve the efficiency of processing the lithium ion battery scrap.

  As a result of intensive studies on the leaching mode of each element when the lithium ion battery scrap is leached with an acidic solution, the manganese in the lithium ion battery scrap added to the acidic solution is dissolved into manganese ions. It has been found that by contacting the target metal in the lithium ion battery scrap, the manganese ions are precipitated as manganese dioxide and promote the leaching of the target metal. In addition, when manganese dioxide is added to the acidic solution separately at this time, the added manganese dioxide becomes a nucleus, and a new finding that the precipitation reaction in which the manganese ions in the acidic solution become manganese dioxide proceeds. Obtained.

  From this, by adding manganese dioxide to the acidic solution at an appropriate time, the precipitation reaction in which the manganese ions in the acidic solution become manganese dioxide, and the accompanying leaching of the target metal, are promoted, and lithium ions We thought that the leaching time of battery scrap could be shortened effectively.

  Under such knowledge, the lithium ion battery scrap leaching method of the present invention is a method of leaching lithium ion battery scrap containing at least the target metal in an acidic solution, and in the state where manganese ions are present in the acidic solution. In addition, manganese ion and manganese dioxide are simultaneously present in the acidic solution by adding manganese dioxide to the acidic solution.

  Here, in the present invention, prior to addition of manganese dioxide to the acidic solution, adding a solution containing manganese ions to the acidic solution, leaching manganese from the lithium ion battery scrap further containing manganese, and / or Alternatively, it is preferable that manganese ions are generated and present in the acidic solution by adding a material containing manganese to the acidic solution and leaching manganese from the material.

  Here, prior to addition of manganese dioxide to the acidic solution, leaching manganese from the lithium ion battery scrap further containing manganese, and / or adding a material containing manganese to the acidic solution from the material When manganese ions are produced and present in the acidic solution by leaching manganese, it is preferable to add hydrogen peroxide to the acidic solution when leaching the manganese.

  Further, the leaching method of lithium ion battery scrap of the present invention is a method of leaching lithium ion battery scrap containing at least a target metal with an acidic solution, wherein the acidic solution is free from manganese ions in the acidic solution. Manganese dioxide is added to the solution, and then manganese ions are generated in the acidic solution, whereby manganese ions and manganese dioxide are simultaneously present in the acidic solution.

  Here, after addition of manganese dioxide to the acidic solution, adding a solution containing manganese ions to the acidic solution, leaching manganese from lithium ion battery scrap further containing manganese, and / or to the acidic solution It is preferable to generate manganese ions in the acidic solution by adding a material containing manganese and leaching manganese from the material.

  Also, here, after adding manganese dioxide to the acidic solution, leaching manganese from the lithium ion battery scrap further containing manganese, and / or adding a material containing manganese to the acidic solution, In the case where manganese ions are present in the acidic solution by leaching, it is preferable to add hydrogen peroxide to the acidic solution when leaching the manganese.

In any of the leaching methods described above, when the manganese ions and manganese dioxide are simultaneously present in the acidic solution, the concentration of the manganese ions in the acidic solution decreases, or when the manganese ions disappear, the acidic solution Adding a solution containing manganese ions to a lithium ion battery scrap further containing manganese and / or adding a material containing manganese to the acidic solution to leach manganese from the material Thus, it is preferable to produce manganese ions in the acidic solution.
The material containing manganese can be manganese dioxide.

In the above leaching method, if no further manganese ions are formed in the acidic solution thereafter, manganese ions and manganese dioxide are simultaneously present in the acidic solution, and no hydrogen peroxide solution is present in the acidic solution. Is preferable.
Thereafter, when no further manganese ions are generated in the acidic solution, manganese ions and manganese dioxide are present in the acidic solution at the same time, and at least the amount of manganese ions in the acidic solution is necessary for leaching of the target metal. Is preferably present.

After the target metal is leached, the leaching residue containing manganese dioxide can be separated and recovered from the liquid after leaching.
Further, as the manganese dioxide added to the acidic solution, a leaching residue obtained by leaching lithium ion battery scrap containing at least the target metal and manganese can be used.

The target metal may be one or more of nickel and cobalt.
The valuable metal recovery method of the present invention is to recover nickel and / or cobalt from the leached solution obtained by any of the above-described lithium ion battery scrap leaching methods.

According to the leaching method of lithium ion battery scrap of the present invention, manganese dioxide is added to the acidic solution, and manganese ions and manganese dioxide are simultaneously present in the acidic solution regardless of which one is present first, The reaction in which the manganese ions in the acidic solution become manganese dioxide is promoted, and accordingly, the leaching of the target metal into the acidic solution is also promoted, so that the leaching time of the target metal can be shortened. .
Thereby, the efficiency of processing of lithium ion battery scrap can be improved.

It is a schematic diagram which shows one Embodiment of the leaching method of this invention. It is a schematic diagram which shows other embodiment of the leaching method of this invention. It is process drawing which shows roughly an example of the recovery method of a valuable metal which can use the leaching method of this invention. It is process drawing which shows roughly the other example of the recovery method of a valuable metal which can use the leaching method of this invention. It is a graph which shows transition of the leaching rate of each metal accompanying progress of leaching time in a comparative example. It is a graph which shows transition of the leaching rate of each metal with progress of leaching time in the example of an invention.

Hereinafter, embodiments of the present invention will be described in detail.
The method for leaching lithium ion battery scrap according to one embodiment of the present invention is a method for leaching lithium ion battery scrap containing at least a target metal with an acidic solution. Here, when manganese ions are present in the acidic solution to which the scrap of the lithium ion battery is added, the manganese ions and the target metal come into contact with each other, and the leaching of the target metal is promoted based on their oxidation-reduction reaction. The manganese ions are precipitated as manganese dioxide.

  In order to allow the precipitation reaction of manganese ions accompanying the leaching promotion of the target metal to be performed in a short time, in this embodiment, manganese dioxide is separately added to the acidic solution, and manganese ions and manganese dioxide are added to the acidic solution. Are present at the same time. According to this, the added manganese dioxide greatly accelerates the reaction in which the manganese ions in the acidic solution become manganese dioxide with the leaching of the target metal. As a result, the leaching time of the target metal can be shortened. The details will be described below.

(Lithium ion battery scrap)
The lithium ion battery scrap targeted in the present invention is a so-called battery container, a positive electrode material with an aluminum foil or a positive electrode active material, or at least one of these, discarded due to the life of the battery product, manufacturing defects or other reasons Alternatively, for example, a battery case or the like can be roasted, chemically treated, crushed, and / or sieved, as described later, as necessary. However, such roasting, chemical treatment, crushing, and sieving are not necessarily required depending on the type of lithium ion battery scrap.

Here, for example, when the lithium ion battery scrap is a battery case, this lithium ion battery scrap is generally a single metal oxide composed of one element of lithium, nickel, cobalt, and manganese constituting the positive electrode active material. Aluminum, copper, iron, and the like may be included in addition to a composite metal oxide composed of a material and / or two or more elements.
Alternatively, in the case of a positive electrode active material, the scrap can generally include the above single metal oxide and / or composite metal oxide. Moreover, in the case of the positive electrode material with an aluminum foil, aluminum may be further contained in addition to the single metal oxide and / or the composite metal oxide.
The target metal to be leached by the leaching method of the present invention can be at least cobalt and / or nickel, preferably cobalt and nickel, among the above metals that can be included in the lithium ion battery scrap.

(Scrap leaching method)
When the powdered or granular lithium ion battery scrap as described above is added to an acidic solution such as sulfuric acid and leached, in this embodiment, manganese dioxide is added to the acidic solution, and manganese ions are added to the acidic solution. And manganese dioxide to be added are present simultaneously.
Manganese ions in the acidic solution themselves precipitate as manganese dioxide crystals while promoting leaching of the target metal by an oxidation-reduction reaction with the target metal contained in the lithium ion battery scrap. In such a precipitation reaction of manganese ions, when manganese dioxide is added to the acidic solution, the added manganese dioxide becomes a crystal nucleus and promotes the precipitation reaction. Thereby, the leaching of the target metal is greatly promoted, and most of the target metal can be leached in a short time.

  Specifically, in order to make the added manganese dioxide and manganese ions exist in the acidic solution at the same time, it can be divided into two cases shown in FIGS. That is, FIG. 1 shows the case where manganese ions are already present in the above acidic solution and manganese dioxide is added in that state, and FIG. 2 shows the addition of manganese dioxide in the absence of manganese ions in the acidic solution. Then, the case where manganese ions are generated in the acidic solution is shown. The lithium ion battery scrap may be added to the acidic solution at any stage, but it may be added before or during the above precipitation reaction of manganese ions. It is effective from the viewpoint of promoting leaching.

  In the case shown in FIG. 1 (when manganese dioxide is added in a state where manganese ions are present in the acidic solution), manganese ions are previously present in the acidic solution, so that manganese ions are added to the acidic solution prior to the addition of manganese dioxide. Adding lithium-containing battery scraps to the acidic solution when lithium-ion battery scrap contains manganese in addition to the target metal, and leaching the manganese into the acidic solution, adding manganese-containing materials to the acidic solution By performing at least one of the operations for leaching manganese in the material, manganese ions can be generated in the acidic solution before the addition of manganese dioxide.

On the other hand, in the case shown in FIG. 2 (when manganese dioxide is added in a state where manganese ions are not present in the acidic solution and then manganese ions are generated in the acidic solution), manganese ions are added to the acidic solution after the addition of manganese dioxide. In order to make it exist, after adding manganese dioxide, work to add a solution containing manganese ions to the acidic solution, and when the lithium ion battery scrap further contains manganese in addition to the target metal, add the lithium ion battery scrap to the acidic solution The manganese solution is added to the acidic solution after the addition of manganese dioxide by performing at least one of the operation of leaching the manganese and adding the material containing manganese to the acidic solution and leaching the manganese in the material. Ions can be generated.
That is, in any case shown in FIGS. 1 and 2, manganese ions can be generated and exist in the acidic solution by employing at least one of the above three operations.

  Of these, in the work of leaching manganese contained in lithium-ion battery scrap and the work of adding materials containing manganese to the acidic solution, hydrogen peroxide is added to the acidic solution to promote the leaching of manganese. It is effective. Thereby, the production | generation of the manganese ion in an acidic solution can be performed in a short time. As used herein, “material containing manganese” means a material containing manganese alone and / or manganese oxide, chloride, sulfide, hydroxide, carbonate or other compounds. It may be.

  On the other hand, hydrogen peroxide solution may react with manganese dioxide added or generated in an acidic solution to cause leaching of manganese dioxide. Therefore, when hydrogen peroxide is added, manganese ions and manganese dioxide are present simultaneously in the acidic solution, and no further manganese ions are generated in the acidic solution. It is desirable to adjust the amount of the hydrogen peroxide solution so that the manganese ion concentration at the highest level is the amount necessary for the leaching of the target metal. If hydrogen peroxide solution is present in the acidic solution at this time, even manganese dioxide may be leached with hydrogen peroxide solution, thereby increasing the manganese ions promoted by the added manganese dioxide. This is because the precipitation reaction may not proceed in a short time as expected.

  From such a viewpoint, when hydrogen peroxide solution is used, it is preferable to add manganese dioxide after the hydrogen peroxide solution in the acidic solution disappears. Actually, after adding a certain amount of time after adding hydrogen peroxide solution to the acidic solution, manganese in the acidic solution is leached and the hydrogen peroxide solution is sufficiently consumed, so that the oxidation and reduction in the acidic solution is performed. When the potential (ORP) is stable, manganese dioxide can be added to the acidic solution. For example, manganese dioxide can be added after 0 hours to 12 hours, preferably 0.5 hours to 1 hour have elapsed since the addition of hydrogen peroxide.

  In addition, in the operation of adding a solution containing manganese ions to the acidic solution, the solution containing manganese ions to be added can be a sulfuric acid solution or the like in which manganese is leached. There is no.

As described above, when manganese ions and manganese dioxide are simultaneously present in the acidic solution, when no further manganese ions are subsequently formed in the acidic solution, that is, most manganese ions throughout the leaching process. When manganese ions and manganese dioxide are present at the same time, it is preferable that manganese ions in the acidic solution be present in an amount necessary for leaching of the target metal.
The amount of such manganese ions varies depending on the target leaching rate of the target metal to be finally leached. The amount of manganese ions required for leaching the target metal is, for example, when the target leaching rate is 90% or more, the amount of manganese ions at the highest concentration throughout the leaching process, and the undissolved target. It can be set to an amount in which the number of moles is equal to the amount obtained by removing 10% of the target metal contained in the scrap from the amount of metal.
When the leaching of the target metal is completed, the manganese ions in the acidic solution are all manganese dioxide, which can reduce the man-hours and costs required to recover manganese from the leached solution in a later step described later. preferable.

  Manganese dioxide to be added acts as a crystal nucleus in a reaction in which manganese ions in the acidic solution are precipitated as manganese dioxide crystals. Therefore, although the addition amount of manganese dioxide is not so important, for example, manganese dioxide can be added in an amount ranging from 10% to 100% by mass ratio with respect to the lithium ion battery scrap. If the added amount of manganese dioxide is large, the time and effort for subsequent collection by filtration or the like will increase. On the other hand, if the added amount is small, the effect may not be sufficiently exhibited.

  The manganese dioxide added to the acidic solution may be accompanied by other materials such as cobalt sulfate and nickel sulfate. That is, if the additive added to the acidic solution contains at least manganese dioxide, the reaction of manganese ions in the acidic solution can be promoted as described above.

  In addition, after setting it as the state in which manganese dioxide and manganese ion exist simultaneously in an acidic solution, an acidic solution can be stirred at a stirring speed of 0 rpm to 750 rpm at a temperature of 20 ° C. to 80 ° C., if necessary. it can.

  After the manganese ions and manganese dioxide exist in the acidic solution at the same time, the manganese ions in the acidic solution required to promote the leaching of the target metal are reduced before the target metal is sufficiently leached. Or if manganese ions in the acidic solution disappear, the manganese ions are increased in the acidic solution, so the addition of the solution containing manganese ions to the acidic solution, the leaching of manganese in the lithium ion battery scrap, and / or Alternatively, a material containing manganese can be added to the acidic solution. Thereby, the precipitation reaction of manganese ions can be maintained until the leaching of the target metal is completed.

By the way, the target metal to be leached by this leaching method can be one or more of nickel and cobalt as described above. When these target metals come into contact with the metal ions of manganese that have a lower redox equilibrium potential and are leached first, leaching in an acidic solution is effectively promoted.
Since manganese is a metal that can take different oxidation numbers, the above target metal can be dissolved effectively, and it can be oxidized and precipitated as an oxide.

After leaching the target metal in this manner, the obtained post-leaching liquid and leaching residue can be separated by, for example, solid-liquid separation.
Here, since the leaching residue includes added manganese dioxide and manganese dioxide precipitated by contact of manganese ions in the acidic solution with the target metal, it is preferable to collect the leaching residue. Furthermore, it is more preferable to use this leaching residue as manganese dioxide added to the acidic solution as described above from the viewpoint of cost reduction by reusing manganese dioxide.

The leaching method as described above can be used for a method for recovering valuable metals from lithium ion battery scrap.
In this recovery method, as illustrated in FIGS. 3 and 4, a leaching step for leaching lithium ion battery scrap and a recovery step for recovering the target metal and the like from the leached solution obtained in the leaching step are sequentially performed. In addition, prior to the leaching step, a roasting step, a sieving step, and the like can be performed, but these roasting step and sieving step are not necessarily performed. Each step will be described below.

(Roasting process)
The discarded lithium ion battery scrap can be roasted by a known method if necessary. Thereby, the unnecessary substance contained in the scrap can be decomposed, burned or volatilized. As a heating furnace for performing roasting, a fixed bed furnace, an electric furnace, a heavy oil furnace, a kiln furnace, a stalker furnace, a fluidized bed furnace, or the like can be used.

  In addition, it is possible to perform the required chemical treatment together with such roasting, and after adjusting to an appropriate size by crushing scrap using a uniaxial crusher or a biaxial crusher, etc., the following The sieving step can be carried out.

(Sieving process)
In this sieving step, a portion of aluminum or the like can be removed by sieving the scraps after being crushed as described above. In order to effectively screen, it is desirable to perform the above-described heat treatment and chemical treatment on the scrap in advance.
Although this sieving is not essential, if sieving is not performed, the amount of reagent used in acid leaching or neutralization in the leaching process may increase.

(Leaching process)
The leaching step can be performed according to the leaching method described above. In this leaching step, the addition of manganese dioxide to the acidic solution can significantly reduce the leaching time, so that the metal recovery efficiency can be greatly improved. Moreover, since the liquid after leaching in which the target metal is sufficiently leached can be obtained here, the metal can be recovered at a high recovery rate in the recovery step described later.

(Recovery process)
After the leaching step, a collecting step for collecting a metal such as a target metal from the leached solution is performed. More specifically, depending on the metal element contained in the lithium ion battery scrap, for example, the steps illustrated in FIG. 3 or 4 can be included.

  In this recovery step, after the leaching solution obtained in the leaching step, for example, using a general solvent extraction method or electrolysis method, etc., each element including the target metal dissolved therein is recovered, If manganese remains in the dissolved state after the leaching, manganese is separated from the target metal and recovered.

In the place shown in FIG. 3, among lithium, nickel, cobalt, manganese, aluminum, copper, iron, etc. contained in the lithium ion battery scrap and dissolved in the leaching solution, first, iron and aluminum are subjected to solvent extraction. .
Subsequently, manganese and copper are recovered from the resulting solution. However, here, as described above, the amount of manganese contained in the solution decreases due to the precipitation of manganese dioxide in the leaching step. Or depending on conditions, manganese may not be contained in the solution, and in this case, recovery of manganese becomes unnecessary. As a result, the cost required for recovery of manganese here can be effectively reduced or reduced.
Thereafter, each of cobalt and nickel can be recovered sequentially, and finally each metal can be recovered leaving lithium in the solution.

  On the other hand, in the place shown in FIG. 4, since the elements contained in the lithium ion battery scrap are only lithium, nickel, cobalt, and manganese, manganese, cobalt, and nickel are sequentially recovered from the liquid after leaching, and only lithium is recovered. By using the remaining solution, it can be performed more easily than the method shown in FIG. If the metal dissolved in the solution after leaching does not contain manganese, it is not necessary to collect manganese in the recovery process.

  Next, the collection method of the present invention was experimentally implemented and will be described below. However, the description here is for illustrative purposes only and is not intended to be limiting.

  While adding 10 g of the positive electrode active material A as a lithium ion battery scrap containing manganese, cobalt, nickel and lithium in amounts shown in Table 1, to 100 ml of pure water and a sulfuric acid acidic solution of 1 molar equivalent of sulfuric acid, To this sulfuric acid acidic solution, 0.42 times molar equivalent of hydrogen peroxide was added and stirred at a stirring speed of 250 rpm at a leaching temperature of 60 ° C. to leach out each metal.

Here, Mn, Ni, Co and H ₂ SO ₄ react at a molar ratio of Mn, Co, Ni: H ₂ SO ₄ = 1: 1, and Li and H ₂ SO ₄ become Li: H ₂ SO. _The reaction was carried out at a molar ratio of ₄ = 1: 2, and the total of these H ₂ SO ₄ was set to 1-fold molar equivalent. In addition, Mn, Ni, Co and H ₂ O ₂ are reacted at a molar ratio of Mn, Ni, Co: H ₂ O ₂ = 2: 1, and the total H ₂ O _{2 is set} to 1 time molar equivalent. .
2LiMO ₂ + 3H ₂ SO ₄ + H ₂ O ₂ → 2MSO ₄ + LiSO ₄ + O ₂ + 4H ₂ O
(M: Mn, Ni, Co)

Here, in the inventive example, 10 g of a leaching residue separately obtained as manganese dioxide was added after 1 hour from the addition of the hydrogen peroxide solution. On the other hand, manganese dioxide was not added in the comparative example.
The transition of the leaching rate of each metal with the passage of the leaching time in each of the comparative examples and the invention examples is shown in graphs in FIGS. 5 and 6, respectively.

From the results shown in FIGS. 5 and 6, it is clear that in the inventive example, the addition of manganese dioxide significantly reduced the leaching time compared to the comparative example.
Therefore, it has been found that according to the leaching method according to the present invention, it is possible to shorten the time required for leaching the target metal contained in the lithium ion battery scrap and contribute to the improvement of the processing efficiency.

Under such knowledge, the lithium ion battery scrap leaching method of the present invention is a method of leaching lithium ion battery scrap containing at least the target metal in an acidic solution, and in the state where manganese ions are present in the acidic solution. by adding manganese dioxide to the acidic solution, at the same time the presence of manganese ions and manganese dioxide in an acidic solution, in Rukoto to precipitate the manganese ions.

In the above leaching method, after that, when the concentration of manganese ions is the highest throughout the leaching from the start to the end of the leaching of lithium ion battery scrap, and no further manganese ions are generated in the acidic solution, It is preferable that no hydrogen peroxide is present in the acidic solution in a state where manganese ions and manganese dioxide are simultaneously present in the acidic solution.
Thereafter, when the concentration of manganese ions is the highest throughout the leaching from the beginning to the end of the leaching of lithium ion battery scrap, and no further manganese ions are generated in the acidic solution, manganese ions are contained in the acidic solution. It is preferable that manganese ions in the acidic solution are present at least in an amount necessary for leaching of the target metal in a state where manganese and manganese dioxide are present simultaneously.

According to leaching method of the lithium ion battery scrap of the present invention, the addition of manganese dioxide in an acidic solution, manganese ions and manganese dioxide in an acidic solution, by the presence at the same time, manganese ions in an acidic solution is manganese dioxide As a result, the leaching of the target metal in the acidic solution is also promoted, so that the leaching time of the target metal can be shortened.
Thereby, the efficiency of processing of lithium ion battery scrap can be improved.

It is a schematic diagram which shows one Embodiment of the leaching method of this invention. It is a schematic diagram showing a leaching how the reference example. It is process drawing which shows roughly an example of the recovery method of a valuable metal which can use the leaching method of this invention. It is process drawing which shows roughly the other example of the recovery method of a valuable metal which can use the leaching method of this invention. It is a graph which shows transition of the leaching rate of each metal accompanying progress of leaching time in a comparative example. It is a graph which shows transition of the leaching rate of each metal with progress of leaching time in the example of an invention.

Claims (14)

  A method of leaching lithium ion battery scrap containing at least a target metal in an acidic solution, wherein manganese ions are added to the acidic solution in a state where manganese ions are present in the acidic solution. A method for leaching lithium ion battery scrap in which manganese ions and manganese dioxide are present simultaneously.   Prior to adding manganese dioxide to the acidic solution, adding a solution containing manganese ions to the acidic solution, leaching manganese from the lithium ion battery scrap further containing manganese, and / or manganese in the acidic solution The method of leaching lithium ion battery scrap according to claim 1, wherein a manganese ion is produced and present in the acidic solution by adding a material containing leaching and leaching manganese from the material.   Prior to the addition of manganese dioxide to the acidic solution, leaching manganese from the lithium ion battery scrap further containing manganese and / or adding a material containing manganese to the acidic solution to leach manganese from the material The method of leaching lithium ion battery scrap according to claim 1, wherein manganese ions are generated and present in the acidic solution, and hydrogen peroxide is added to the acidic solution when leaching the manganese.   A method of leaching lithium ion battery scrap containing at least a target metal in an acidic solution, wherein manganese acid is added to the acidic solution in a state where manganese ions are not present in the acidic solution, and then in the acidic solution A method for leaching lithium ion battery scrap, in which manganese ions and manganese dioxide are simultaneously present in an acidic solution by producing manganese ions in the battery.   After adding manganese dioxide to the acidic solution, adding a solution containing manganese ions to the acidic solution, leaching manganese from a lithium ion battery scrap further containing manganese, and / or containing manganese in the acidic solution The method for leaching lithium ion battery scrap according to claim 4, wherein manganese ions are generated in the acidic solution by adding materials and leaching manganese from the materials.   After the addition of manganese dioxide to the acidic solution, leaching manganese from the lithium ion battery scrap further containing manganese and / or adding a material containing manganese to the acidic solution to leach manganese from the material 5. The method for leaching lithium ion battery scrap according to claim 4, wherein manganese ions are present in the acidic solution, and hydrogen peroxide is added to the acidic solution when leaching the manganese.   After the manganese ions and manganese dioxide are simultaneously present in the acidic solution, when the manganese ion concentration in the acidic solution decreases or disappears, a solution containing manganese ions is added to the acidic solution. Leaching manganese from lithium ion battery scrap further containing manganese, and / or adding manganese-containing material to the acidic solution to leach manganese from the material, thereby leaching manganese ions into the acidic solution. The method for leaching lithium ion battery scrap according to any one of claims 1 to 6, wherein:   The method for leaching lithium ion battery scrap according to any one of claims 2, 3, and 5 to 7, wherein the material containing manganese is manganese dioxide.   The hydrogen peroxide solution is not present in the acidic solution in a state where no further manganese ions are generated in the acidic solution, manganese ions and manganese dioxide are simultaneously present in the acidic solution. The method for leaching lithium ion battery scrap according to claim 1.   No further manganese ions are produced in the acidic solution, and the manganese ions in the acidic solution are present at least in the amount necessary for the leaching of the target metal, with the manganese ions and manganese dioxide simultaneously present in the acidic solution. Item 10. The method for leaching lithium ion battery scrap according to any one of Items 1 to 9.   The leaching method for lithium ion battery scrap according to any one of claims 1 to 10, wherein after the leaching of the target metal, a leaching residue containing manganese dioxide is separated and recovered from the liquid after leaching.   The lithium ion battery scrap according to any one of claims 1 to 11, wherein a leaching residue obtained by leaching a lithium ion battery scrap containing at least a target metal and manganese is used as the manganese dioxide added to the acidic solution. Leaching method.   The method for leaching lithium ion battery scrap according to any one of claims 1 to 12, wherein the target metal is one or more of nickel and cobalt.   A method for recovering valuable metals, wherein nickel and / or cobalt is recovered from the post-leaching solution obtained by the method for leaching lithium ion battery scraps according to any one of claims 1 to 13.