Active material, method for producing regenerated active material, method for tracking valuable element recovered from battery, and compound for tracking

Abstract

The active material of the present invention contains at least one element M selected from the group consisting of nickel, cobalt, manganese, and lithium, and an element X different from the element M. Element X is a metal selected from the group consisting of Group 2 and Group 15 in the second cycle of the periodic table, Group 3, Group 11 and Group 13 to Group 16 in the fourth cycle, Group 1 to Group 3, Group 7 to Group 13 and Group 15 to Group 17 in the fifth cycle, Group 1 to Group 3 and Group 7 to Group 17 in the sixth cycle, and Group 7 to Group 17 in the sixth cycle. And at least one element among metals of Groups 1 to 17 in the seventh period.

Description

Technical Field

[0001] The present invention relates to an active material. In addition, the present invention relates to a method for producing a regenerated active material. Further, the present invention relates to a method for tracing and investigating valuable elements recovered from a battery and a compound for tracing and investigating. Background Art

[0002] In recent years, secondary batteries have attracted much attention as an initiative to prevent global warming by reducing CO2. Materials used in such secondary batteries include materials using various valuable elements. For example, lithium-ion batteries generally contain valuable elements such as nickel, cobalt, and lithium. From the perspective of effective utilization of resources and reduction of environmental burden, research is being conducted on the recycling and reuse of valuable elements.

[0003] For example, Patent Document 1 proposes a method for recovering lithium from waste lithium-ion batteries. Patent Document 2 attempts to recover lithium from roasted waste lithium-ion batteries by leaching and neutralization separation. Patent Document 3 proposes a method for reducing the grade of copper and carbon from the negative electrode contained in the recovered material when recovering cobalt and nickel contained in the battery.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2019-99901

[0007] Patent Document 2: Japanese Patent Application Publication No. 2019-160429

[0008] Patent Document 3: Japanese Patent Application Publication No. 2020-64855 Summary of the invention

[0009] In recent years, there has been an increasing focus on SDGs (Sustainable Development Goals), and the momentum for recycling valuable elements in battery materials has become increasingly evident. For example, the battery regulation proposed by the European Commission in 2020 requires that batteries be accompanied by documents to show that the amount of cobalt, nickel, and lithium from recycled materials has reached a minimum proportion. In addition, the regulation requires that elements such as cobalt, nickel, and lithium be identified and tracked for each battery, and that these elements be managed in a database.

[0010] However, in the methods for recovering valuable elements known so far, the tracking or traceability of the recovered elements is not sufficient, and it is not easy to comply with recycling regulations expected in the future.

[0011] The technical problem underlying the present invention is therefore to improve the tracking or traceability of valuable elements recovered from batteries.

[0012] The present invention provides an active material, comprising: at least one element M selected from the group consisting of nickel, cobalt, manganese and lithium, and an element X different from the element M,

[0013] The element X is at least one element selected from the group consisting of metals of Group 2 and Group 15 in Period 2 of the periodic table, metals of Group 3, Group 11, and Groups 13 to 16 in Period 4, metals of Groups 1 to 3, Groups 7 to 13, and Groups 15 to 17 in Period 5, metals of Groups 1 to 3 and Groups 7 to 17 in Period 6, and metals of Groups 1 to 17 in Period 7.

[0014] In addition, the present invention provides a method for producing a regenerated active material, which uses an element M recovered from a battery having an active material a containing an element M as a raw material to produce an active material b of the same type or a different type as the active material a, wherein the element M is at least one selected from the group consisting of nickel, cobalt, manganese and lithium.

[0015] As the active material a, an active material further containing an element X is used, wherein the element X is at least one selected from the group consisting of metals of Group 2 and Group 15 in Period 2 of the periodic table, metals of Group 3, Group 11, and Groups 13 to 16 in Period 4, metals of Groups 1 to 3, Groups 7 to 13, and Groups 15 to 17 in Period 5, metals of Groups 1 to 3 and Groups 7 to 17 in Period 6, and metals of Groups 1 to 17 in Period 7.

[0016] In addition, the present invention provides a method for tracing and investigating valuable elements recovered from a battery, wherein, when an active material b of the same kind or different kind as the active material a is manufactured using the element M recovered from a battery having an active material a containing the element M as a raw material, an active material further containing the element X is used as the active material a, and the element M recovered from the battery containing the active material b is traced and investigated based on the type and / or amount of the element X contained in the active material b, wherein the element M is at least one selected from the group consisting of nickel, cobalt, manganese and lithium, and the element X is at least one selected from the group consisting of metals of Group 2 and Group 15 in Period 2 of the periodic table, metals of Group 3, Group 11 and Groups 13 to 16 in Period 4, metals of Groups 1 to 3, Groups 7 to 13 and Groups 15 to 17 in Period 5, metals of Groups 1 to 3 and Groups 7 to 17 in Period 6, and metals of Groups 1 to 17 in Period 7.

[0017] In addition, the present invention provides a method for tracing and investigating valuable elements recovered from a battery, wherein, when an active material b of the same or different type as the active material a is manufactured using the element M recovered from a battery having an active material a containing the element M as a raw material, an active material further containing an element X is used as the active material a, and the element M recovered from the battery containing the active material b is traced and investigated based on the type and / or amount of the element X contained in the active material b, wherein the element M is at least one selected from the group consisting of nickel, cobalt, manganese and lithium, and the element X is not contained in the natural mineral that is the raw material of the element M and does not participate in the battery reaction of the battery containing the active material b.

[0018] Furthermore, the present invention provides a compound for tracking and investigating valuable elements recovered from a battery, wherein, when an active material b of the same or different type as the active material a is manufactured using an element M recovered from a battery having an active material a containing the element M as a raw material, the compound for tracking and investigating is added to the active material a, and is used to track and investigate the element M recovered from the battery containing the active material b, wherein the element M is at least one selected from the group consisting of nickel, cobalt, manganese and lithium,

[0019] The compound for follow-up investigation contains element X, which is at least one selected from metals of Group 2 and Group 15 in Period 2 of the periodic table, metals of Group 3, Group 11, and Groups 13 to 16 in Period 4, metals of Groups 1 to 3, Groups 7 to 13, and Groups 15 to 17 in Period 5, metals of Groups 1 to 3 and Groups 7 to 17 in Period 6, and metals of Groups 1 to 17 in Period 7.

[0020] Furthermore, the present invention provides a compound for tracking and investigating valuable elements recovered from a battery, wherein, when an active material b of the same or different type as the active material a is manufactured using an element M recovered from a battery having an active material a containing the element M as a raw material, the compound for tracking and investigating is added to the active material a, and is used to track and investigate the element M recovered from the battery containing the active material b, wherein the element M is at least one selected from the group consisting of nickel, cobalt, manganese and lithium,

[0021] The traceability compound includes an element X that is not included in a natural mineral that is a raw material of the element M and does not participate in a battery reaction of a battery including the active material b. DETAILED DESCRIPTION

[0022] The present invention is described below based on a preferred embodiment. The present invention relates to an active material for a battery. The active material is capable of tracing valuable elements contained in the active material or has high traceability. In this specification, tracing refers to determining where the active material containing valuable elements is now and where it existed in the past, in other words, it refers to tracking the situation of the active material containing valuable elements. In addition, in this specification, traceability refers to clarifying the path of the active material containing valuable elements from production to circulation to the destination.

[0023] In the past, product tracking or traceability was achieved by attaching an identification code to the product itself or to the packaging used to package the product, and by using an online tracking system based on the identification code. Since the active material of the battery itself is the subject of commercial transactions and can be circulated independently, it is possible to track it and improve traceability. However, once it is assembled into a battery, it is extremely difficult to track and achieve traceability. However, as mentioned above, in the future, it will be required to identify and track the valuable elements contained in each battery and manage these elements in a database. Therefore, the active material that is the raw material of the battery containing the valuable elements also needs to be able to track the valuable elements contained therein and improve traceability. The active material of the present invention meets this requirement.

[0024] In this specification, the valuable element contained in the active material refers to at least one element M selected from the group consisting of at least nickel, cobalt, manganese and lithium. These elements are part of a group of elements called so-called rare metals, which are widely used as raw materials for batteries. It should be noted that according to the explanation of the Ministry of Economy, Trade and Industry of Japan, rare metals are defined as "metals that exist in small quantities on the earth or are difficult to extract due to technical and economic reasons", and there is currently (and is expected to be) industrial demand, so it is important to ensure a stable supply from a policy perspective.

[0025] In the present invention, the type of active material containing the element M which is a valuable element is not particularly limited, and both positive electrode active materials and negative electrode active materials can be used. As the positive electrode active material, for example, lithium transition metal composite oxides having a layered rock salt structure or a spinel structure can be listed. Specifically, LiCoO2, LiNiO2, LiM n O4 and Li(Co 1 / 3 Ni 1 / 3 Mn 1 / 3 )O2, etc. In addition, it can be LiFePO4, etc. On the other hand, as the negative electrode active material, metallic lithium, lithium alloys and lithium titanate, etc. can be listed, but it is not limited to these.

[0026] There is no particular restriction on the type of battery having an active material containing element M, and either a primary battery or a secondary battery can use the active material of the present invention. Considering that element M is at least one of nickel, cobalt, manganese and lithium, in other words, element M is one or more of nickel, cobalt, manganese and lithium, as a typical battery, lithium primary batteries and secondary batteries can be cited for batteries using the active material of the present invention. The electrolyte used for these batteries can be liquid or solid. In the case where the electrolyte is solid, that is, in the case of a solid battery, the solid battery, in addition to a solid battery in which the electrolyte does not contain a liquid substance or a gel-like substance at all, also includes a method in which the electrolyte contains, for example, less than 50% by mass. Less than 30% by mass. Less than 10% by mass of a liquid substance or a gel-like substance.

[0027] The active material of the present invention contains, in addition to the element M belonging to the valuable element, an element X belonging to an element different from the element M. For the purpose of tracking the element M or improving the traceability of the element M, the element X is contained in the active material. That is, the element X is used for the purpose of marking the element M. In detail, by containing the element X in the active material a containing the element M, when the element M recovered from the battery having the active material a is used as a raw material to manufacture an active material b of the same or different type as the active material a, that is, when the element M derived from the active material a is used to manufacture the regenerated active material b, during the manufacture, in addition to the element M derived from the active material a, the element X derived from the active material a is also mixed in the active material b. As a result, it can be known that the active material b is an active material regenerated using the active material a as a raw material. That is, the element M contained in the active material a can be traced and investigated.

[0028] Specifically, when the element X is detected from the active material b by element analysis of the active material b, it can be known that the active material b is an active material regenerated using the element M included in the active material a as a raw material.

[0029] In addition, the source of the element M contained in the active material b can be known from the type of element X. For example, when the element X is X1, it can be determined that the element M contained in the active material b is derived from the active material a1 manufactured by company A, and when the element X is X2, it can be determined that the element M contained in the active material b is derived from the active material a2 manufactured by company B. In this way, by including the element X in the active material, the manufacturing area and manufacturing facility of the active material can be known.

[0030] On this basis or in lieu thereof, by changing the type of element X according to the manufacturing year of the active material, for example, when element X is X1, it can be determined that the element M contained in the active material b originates from the active material a1 manufactured in a certain year, and when element X is X2, it can be determined that it originates from the active material a2 manufactured in another year.

[0031] On this basis or in lieu thereof, the number of times the active material containing element M is recycled can be determined based on the amount of element X contained in the active material b. For example, the greater the amount of element X contained in the active material b, the greater the number of times the active material containing element M is recycled. A greater number of recycling times is also an indicator of the degree of deterioration of the regenerated active material.

[0032] In this way, the active material of the present invention can easily know the distribution history, production site, number of regenerations, etc. of the active material from the time of production by labeling the element M which is a valuable element with the element X.

[0033] There is no particular limitation on the method for recovering the element M from a battery having an active material containing the element M which is a valuable element. For example, the following method can be used: after the battery is roasted, crushed, and further sieved, the powdered battery residue obtained after the sieve is added to a leaching solution for leaching, so that lithium, nickel, cobalt, manganese, etc. that may be contained therein are dissolved in the leaching solution (for example, see Japanese Patent Publication No. 2015-195129).

[0034] Alternatively, the following method may be used: the active material recovered from the battery is cut, heated to volatilize the binder, impact-crushed to peel off the active material, and separated into the current collector and the active material by a vibrating screen (see, for example, Japanese Patent Application Publication No. 2013-211234).

[0035] Furthermore, a method may be adopted in which the battery is subjected to heat treatment to remove organic matter, the outer casing is cut and removed, the active material is crushed, and the current collector and active material are separated by a vibrating screen (see, for example, Japanese Patent Application Publication No. 2013-80595).

[0036] Furthermore, the following method can be adopted: used batteries are pre-baked to remove organic matter and then crushed and sieved to separate blocks mainly consisting of collectors and powders mainly consisting of active materials, the powders are oxidatively calcined and then reduction-calcined to metallize Co and Ni, while iron and manganese are made into oxides and formed into slurry, the slurry is magnetically separated, and the magnetic substances (Co and Ni) are separated and recovered (for example, Japanese Patent Gazette No. 2012-229481).

[0037] The element M recovered by the above method contains trace elements X contained in the active material a as the original active material in the form of accompanying elements M. Next, the precursor of the regenerated active material (the above-mentioned active material b) is obtained using the recovered simple substance of the element M or a compound containing the element M. When the element M is, for example, cobalt or manganese, as the compound containing these elements, for example, cobalt sulfate or manganese sulfate can be used.

[0038] Alternatively, when element M is recovered by the above method, element X or a compound containing element X may be mixed with element M or a compound containing element M to obtain a precursor of the regenerated active material (active material b).

[0039] The precursor is treated by a known method to produce an active material b as a regenerated active material. That is, according to the present invention, a method for producing a regenerated active material b is also provided. In addition to the element M, the active material b contains the element X contained in the active material a as the original active material in the form of a companion element M.

[0040] The existence form of the element X contained in the active material a or the active material b is not particularly limited. For example, it may exist as a constituent element of the active material a or the active material b, or it may exist independently of the active material a or the active material b. It should be noted that when the element X exists as a constituent element of the active material a or the active material b, the element X may be solid-dissolved.

[0041] By repeating the above series of operations, each time the element M that is a valuable element contained in the active material is recycled, the element M can be labeled with the element X. Alternatively, when the element M is recycled, it can be distinguished between the case where the element M is labeled with the element X and the case where the element X is not used. Alternatively, when the element M is recycled, X1 can be used as the element X in the first recycling, and X2 different from X1 can be used as the element X in the second recycling.

[0042] In order to track the active material of the present invention and improve traceability, it is advantageous to be able to clearly identify the element X contained in the active material in distinction from the element M. From this viewpoint, it is preferred that the element X is not contained in the natural mineral that is the raw material of the element M. By adding the element X that is not originally contained in the natural mineral to the active material containing the element M extracted from the natural mineral, the element X can be clearly identified in distinction from the element M.

[0043] The natural minerals that are raw materials of element M are, for example, cobaltite (Co3S4), cobaltite (CoAsS), arsenic cobaltite ((Co, Fe)AsS), pyrocobaltite ((Co, Ni)As3-x )wait.

[0044] When the element M is nickel, examples thereof include pentlandite ((Fe, Ni)9S8), pyrrhotite (NiAs), and nickel-containing pyrrhotite ((Fe, Ni) 1-x S), silicon nickel ore (Ni6Si4O 10 (OH)8) etc.

[0045] When the element M is manganese, hausmannite (Mn3O 4) , pyrolusite (MnO2), cryptomelane (K(Mn 2+ , Mn 4 + )8O 16 ), rhodochrosite (MnCO3), manganese olivine (Mn2SiO4), rhodonite (MnSiO3), brown manganese ore (Mn 2+ Mn 3+ Si8O 12 )wait.

[0046] When the element M is lithium, examples thereof include lepidolite (K(Al, Li)2(Si, Al)4O 10 (OH, F)2), petalite (LiAlSi4O 10 ), spodumene, etc.

[0047] As the element X used to label the element M, it is preferable to use an element that is not contained in the above-mentioned various natural minerals.

[0048] It is more advantageous that the element X is an element that does not participate in the battery reaction of the battery having an active material containing the element X. Thus, the element X can be used only for the purpose of labeling the element M which is a valuable element. In this specification, the element X does not participate in the battery reaction means that there is no difference in various battery performances between a battery having an active material containing the element X and a battery having an active material not containing the element X.

[0049] From the above viewpoints, preferred examples of the element X include at least one element selected from the following metals. These elements may be used alone or in combination of two or more.

[0050] Metals of Group 2 and Group 15 in Period 2 of the Periodic Table.

[0051] Metals of Groups 3, 11, and 13 to 16 in Period 4 of the Periodic Table.

[0052] Metals of Groups 1 to 3, 7 to 13, and 15 to 17 in Period 5 of the Periodic Table of Elements.

[0053] Metals of Groups 1 to 3 and Groups 7 to 17 in Period 6 of the Periodic Table of Elements.

[0054] Metals from Groups 1 to 17 in Period 7 of the Periodic Table.

[0055] Among the above elements preferably used as element X, particularly preferred elements are, for example, at least one selected from scandium (Sc), yttrium (Y), lanthanum (La), gadolinium (Gd) and lutetium (Lu), from the viewpoint of high recognition relative to element M and not participating in the battery reaction.

[0056] From the viewpoint of maintaining various performances of the battery having the active material while being able to track the element M which is a valuable element and also improving the traceability, it is preferred that the amount of the element X contained in the active material of the present invention is 1 ppm or more and 1000 ppm or less relative to the active material. From the viewpoint that this advantage is more significant, the amount of the element X contained in the active material of the present invention is preferably 40 ppm or more, more preferably 50 ppm or more relative to the active material. On the other hand, the amount of the above-mentioned element X can be, for example, 60 ppm or less, or 80 ppm or less relative to the active material.

[0057] The amount of the element X contained in the active material can be measured by, for example, ICP emission spectrometry.

[0058] A compound containing an element X for marking an element M that is a valuable element is useful as a compound for tracing and investigating the element M recovered from a battery having an active material containing the element M. That is, the compound for tracing and investigating is used for tracing and investigating the element M that is a valuable element recovered from a battery. Specifically, when an active material b of the same or different type as the active material a is manufactured using the element M recovered from a battery having an active material a containing the element M as a raw material, the compound for tracing and investigating is added to the active material a to trace and investigate the element M recovered from the battery containing the active material b.

[0059] When the compound for follow-up investigation is added to the active material containing the element M, it is advantageous to use a compound that does not impair the original performance of the active material. Examples of such compounds include compounds containing at least one of scandium (Sc), yttrium (Y), lanthanum (La), gadolinium (Gd), and lutetium (Lu).

[0060] The amount of the compound for follow-up investigation to be added may be an amount such that the amount of the element X contained in the active material is within the above range.

[0061] As described in detail above, the active material of the present invention can easily conduct a traceability survey of the element M, which is a valuable element, from the past to the future. Therefore, the active material of the present invention can easily cope with the revision of the battery recycling related laws and regulations that may appear in the near future.

[0062] The present invention has been described above based on the preferred embodiment, but the scope of the present invention is not limited to the embodiment. For example, in the embodiment, the target element to be tracked is element M (at least one of nickel, cobalt, manganese and lithium), but on this basis or in lieu thereof, rare metals other than element M may also be tracked.

[0063] Possibility of Industrial Application

[0064] According to the present invention, the tracking or traceability of valuable elements recovered from batteries can be improved. Therefore, according to the present invention, the number of recycling times of valuable elements, the manufacturing region of active materials, the manufacturing age of active materials, etc. can be easily known.

Claims

1. An active material comprising: at least one element M selected from the group consisting of nickel, cobalt, manganese and lithium, and an element X different from the element M, The element X is at least one element selected from the group consisting of metals of Group 2 and Group 15 in Period 2 of the periodic table, metals of Group 3, Group 11, and Groups 13 to 16 in Period 4, metals of Groups 1 to 3, Groups 7 to 13, and Groups 15 to 17 in Period 5, metals of Groups 1 to 3 and Groups 7 to 17 in Period 6, and metals of Groups 1 to 17 in Period 7.

2. The active material according to claim 1, wherein The element X is not contained in natural minerals that are raw materials of the element M and does not participate in a battery reaction of a battery including the active material. The active material according to claim 1 or 2, comprising 1 ppm or more and 1000 ppm or less of the element X.

4. A method for producing a regenerated active material, wherein an element M recovered from a battery having an active material a containing an element M is used as a raw material to produce an active material b of the same or different type as the active material a, wherein the element M is at least one selected from the group consisting of nickel, cobalt, manganese and lithium, As the active material a, an active material further containing an element X is used, wherein the element X is at least one selected from the group consisting of metals of Group 2 and Group 15 in Period 2 of the periodic table, metals of Group 3, Group 11, and Groups 13 to 16 in Period 4, metals of Groups 1 to 3, Groups 7 to 13, and Groups 15 to 17 in Period 5, metals of Groups 1 to 3 and Groups 7 to 17 in Period 6, and metals of Groups 1 to 17 in Period 7.

5. The method for producing a regenerative active substance according to claim 4, wherein: The element X is an element that is not contained in a natural mineral that is a raw material of the element M and does not participate in a battery reaction of a battery including the active material b.

6. A method for tracing and investigating valuable elements recovered from batteries, wherein: When an active material b of the same kind or different kind as the active material a is manufactured using element M recovered from a battery having an active material a containing element M as a raw material, an active material further containing element X is used as the active material a, and a trace investigation is conducted on the element M recovered from the battery containing the active material b according to the type and / or amount of element X contained in the active material b, wherein the element M is at least one selected from the group consisting of nickel, cobalt, manganese and lithium, and the element X is at least one selected from the group consisting of metals of Group 2 and Group 15 in Period 2 of the periodic table, metals of Group 3, Group 11 and Groups 13 to 16 in Period 4, metals of Groups 1 to 3, Groups 7 to 13 and Groups 15 to 17 in Period 5, metals of Groups 1 to 3 and Groups 7 to 17 in Period 6, and metals of Groups 1 to 17 in Period 7.

7. A method for tracing and investigating valuable elements recovered from batteries, wherein: When an active material b of the same kind or different kind as the active material a is manufactured using an element M recovered from a battery having an active material a containing the element M as a raw material, an active material further containing an element X is used as the active material a, and a trace investigation is conducted on the element M recovered from the battery containing the active material b based on the type and / or amount of the element X contained in the active material b, wherein the element M is at least one selected from the group consisting of nickel, cobalt, manganese and lithium, and the element X is not contained in a natural mineral that is a raw material of the element M and does not participate in a battery reaction of the battery containing the active material b.

8. A compound for tracing and investigating valuable elements recovered from batteries, wherein: When an active material b of the same or different type as the active material a is manufactured using an element M recovered from a battery having an active material a containing the element M as a raw material, the compound for follow-up investigation is added to the active material a to conduct a follow-up investigation on the element M recovered from the battery containing the active material b, wherein the element M is at least one selected from the group consisting of nickel, cobalt, manganese and lithium, The compound for follow-up investigation contains element X, and the element X is at least one selected from metals of Group 2 and Group 15 in Period 2 of the periodic table, metals of Group 3, Group 11, and Groups 13 to 16 in Period 4, metals of Groups 1 to 3, Groups 7 to 13, and Groups 15 to 17 in Period 5, metals of Groups 1 to 3 and Groups 7 to 17 in Period 6, and metals of Groups 1 to 17 in Period 7.

9. A compound for tracing and investigating valuable elements recovered from batteries, wherein: When an active material b of the same or different type as the active material a is manufactured using an element M recovered from a battery having an active material a containing the element M as a raw material, the compound for follow-up investigation is added to the active material a to conduct a follow-up investigation on the element M recovered from the battery containing the active material b, wherein the element M is at least one selected from the group consisting of nickel, cobalt, manganese and lithium, The traceability compound includes an element X that is not included in a natural mineral that is a raw material of the element M and does not participate in a battery reaction of a battery including the active material b.