Method for manufacturing recycled material and manufacturing system

Abstract

To separate an electrode mixture from a substrate while suppressing changes in the crystal structure of an active material.SOLUTION: A method for manufacturing a recycled material includes the steps of (a) preparing an electrode including a substrate and an electrode mixture, (b) contacting the electrode with ammonia water, (c) separating the electrode mixture from the substrate, and (d) drying the electrode mixture, in this order. In the step (a), the electrode mixture is attached to at least a portion of the substrate. The substrate includes aluminum. The electrode mixture includes an active material.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a method and a manufacturing system for manufacturing recycled materials.

Background Art

[0002] Japanese Patent Application Laid-Open No. 2017-084681 discloses a method for recovering a positive electrode material.

Prior Art Document

Patent Document

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Electrodes contain various renewable materials. It has been considered to manufacture recycled materials by recovering the renewable materials from the electrodes.

[0005] An electrode includes a base material and an electrode mixture. The electrode mixture adheres to the base material. At the initial stage of the recycling process, it is required to separate the electrode mixture from the base material. However, since the electrode mixture adheres strongly to the base material, it is not easy to separate the electrode mixture from the base material.

[0006] For example, it has been proposed to promote the separation of the electrode mixture from the base material by heating the electrode (see, for example, Patent Document 1). The electrode mixture may include an active material, a binder, and the like. When the electrode mixture is exposed to high temperatures, the constituent components such as the binder may dissolve in the active material. As a result, for example, the crystal structure of the active material may change. If the change in the crystal structure is significant, once the active material is returned to the raw materials (sulfate, oxide, ingot, etc.), resynthesis of the active material may be required. The synthesis process of the active material will be traced back in the order of sulfate, oxide, and ingot. The greater the tracing of the synthesis process, the greater the amount of carbon dioxide generated in the regeneration of the active material may be.

[0007] In the case where the change in the crystal structure of the other party is slight, the active material can be regenerated by a simple process. This regeneration process is also referred to as "direct recycling". From the perspective of reducing environmental impact, direct recycling is desired.

[0008] Therefore, the present disclosure aims to separate the electrode binder from the base material while suppressing the change in the crystal structure of the active material.

Means for Solving the Problems

[0009] Hereinafter, the technical configuration and effects of the present disclosure will be described. However, the mechanism of action in this specification includes assumptions. The mechanism of action does not limit the technical scope of the present disclosure.

[0010] 1. The method for manufacturing a regenerated material includes the following (a) to (d) in this order. (a) Prepare an electrode including a base material and an electrode binder. (b) Bring the electrode into contact with aqueous ammonia. (c) Separate the electrode binder from the base material. (d) Dry the electrode binder. In the above (a), the electrode binder is attached to at least a part of the base material. The base material contains aluminum. The electrode binder contains an active material.

[0011] The surface of the base material is covered with an oxide film (anodized film). The oxide film can be formed by natural oxidation of Al. The electrode binder is attached to the surface (oxide film) of the base material. A large number of penetration paths leading to the interface between the electrode binder and the base material are formed in the electrode. When the electrode comes into contact with aqueous ammonia, the aqueous ammonia can penetrate to the interface between the electrode binder and the base material. At the interface, ammonia can act on the anodized film to form an ammonia complex. When the ammonia complex is formed, the adhesion between the base material and the electrode binder can be significantly reduced. Due to the reduction in adhesion, the electrode binder can be peeled off from the base material without heating. That is, the electrode binder can be separated from the base material while suppressing the change in the crystal structure of the active material.

[0012] Furthermore, by reducing the adhesion force, the electrode composite material can be peeled off from the substrate in a short time. Due to the short treatment time, the reaction between aqueous ammonia and Al (dissolution of Al, generation of hydrogen gas, etc.) can also be reduced. That is, the substrate can be recovered in a state where it is also easy to regenerate.

[0013] In addition, when a strongly alkaline aqueous solution such as a sodium hydroxide solution is used instead of aqueous ammonia, the dissolution of Al may progress even in a short time.

[0014] 2. The method for manufacturing the regenerated material described in the above "1" may include, for example, the following configuration. The aqueous ammonia contains ammonia with a mass fraction of 1 to 28%.

[0015] Hereinafter, unless otherwise specified, the concentration of aqueous ammonia indicates the mass fraction of ammonia. Aqueous ammonia in the concentration range of 1 to 28% is easy to obtain or prepare. Furthermore, in the concentration range of 1 to 28%, unfavorable reactions tend not to occur easily. Examples of unfavorable reactions include dissolution of Al, generation of hydrogen gas, and elution of Li.

[0016] 3. The method for manufacturing the regenerated material described in the above "1" or "2" may include, for example, the following configuration. The active material contains a lithium metal composite oxide.

[0017] For example, when the electrode composite material contains a water-soluble binder, it is also conceivable to separate the electrode composite material and the substrate in water. However, when the active material (lithium metal composite oxide) comes into contact with a large amount of water, Li can elute into the water. That is, a change in the composition of the active material can occur. Furthermore, due to the elution of Li, an alkaline aqueous solution is formed. For example, the treatment cost may increase for the recovery of Li from the alkaline aqueous solution and the disposal of the alkaline aqueous solution.

[0018] Ammonia water is originally alkaline. In ammonia water, the driving force for the elution reaction of Li is considered to be small. That is, in ammonia water, the elution reaction of Li is considered to be difficult to proceed. Therefore, it is expected that an active material with a small composition change will be recovered. Furthermore, a reduction in processing cost is also expected.

[0019] 4. The method for manufacturing the regenerated material according to any one of the above items "1" to "3" may include, for example, the following configuration. The above (b) includes immersing the electrode in ammonia water.

[0020] The contact method between the electrode and ammonia water is arbitrary. As the contact method, for example, immersion, coating, spraying, etc. can be considered.

[0021] 5. The method for manufacturing the regenerated material according to any one of the above items "1" to "4" may include, for example, the following configuration. The above (b) includes applying ammonia water to the electrode.

[0022] 6. The method for manufacturing the regenerated material according to any one of the above items "1" to "5" may include, for example, the following configuration. The above (b) includes spraying ammonia water onto the electrode.

[0023] 7. The method for manufacturing the regenerated material according to any one of the above items "1" to "6" may include, for example, the following configuration. The above (c) includes imparting momentum to the electrode composite material.

[0024] Since the adhesion between the electrode composite material and the base material is reduced, the electrode composite material can be peeled off from the base material by simply imparting momentum (for example, imparting vibration, etc.).

[0025] 8. The method for manufacturing the regenerated material according to any one of the above items "1" to "7" may include, for example, the following configuration. The above (d) includes recovering ammonia from the gas generated during drying.

[0026] Ammonia water may be regenerated from the recovered ammonia. The ammonia water can be reused in the above (b).

[0027] 9. The method for manufacturing a regenerated material according to any one of the above "1" to "8" may further include the following (e) and (f) in this order. (e) Separate the active material from the electrode composite material. (f) Regenerate the active material.

[0028] For example, the active material may be isolated from the electrode composite material. After isolation, the active material may be subjected to a regeneration treatment. In other words, a regenerated active material may be manufactured. Since the change in the crystal structure is small compared to the initial state of the active material, it is expected that the active material can be regenerated by a simple treatment. For example, the active material may be regenerated by replenishing Li to the active material.

[0029] 10. The manufacturing system manufactures a regenerated material from an electrode including a base material and an electrode composite material. The manufacturing system includes a contact device, a separation device, and a drying device. The contact device is configured to bring the electrode into contact with ammonia water. The separation device is configured to separate the electrode composite material from the base material after the contact between the electrode and the ammonia water. The drying device is configured to dry the electrode composite material after the separation of the base material and the electrode composite material.

[0030] 11. The manufacturing system according to the above "10" may further include, for example, a recovery device. The recovery device is configured to recover ammonia from the gas generated by the drying device.

[0031] Hereinafter, embodiments of the present disclosure (hereinafter may be abbreviated as "the present embodiments") will be described. However, the present embodiments do not limit the technical scope of the present disclosure. The present embodiments are illustrative in all respects. The present embodiments are non-limiting. The technical scope of the present disclosure includes all modifications within the meaning and scope equivalent to the description of the claims. For example, any configurations are extracted from the present embodiments and the present examples, and their arbitrary combinations are also initially planned.

Brief Description of the Drawings

[0032]

Figure 1

Figure 2

Figure 3

Figure 4

Modes for Carrying Out the Invention

[0033] <Explanation of Terms> The terms used in this specification are explained. Terms not explained here may be explained each time they are used in this specification.

[0034] Descriptions of "comprising", "including", "having", and variations thereof (such as "consisting of", etc.) are in an open-ended form. The open-ended form may further include additional elements in addition to essential elements, or may not include them. The description of "consisting of" is in a closed form. However, even in the closed form, additional elements that are usually accompanying impurities or are unrelated to the disclosed technology are not excluded. The description of "substantially consisting of" is in a semi-closed form. In the semi-closed form, the addition of elements that do not substantially affect the basic and novel characteristics of the disclosed technology is allowed.

[0035] Expressions such as "may", "can", etc. are used in an allowable sense of "having the possibility of doing" rather than in an obligatory sense of "must do".

[0036] The plurality of steps, operations, and operations included in various methods are not limited to the execution order described, unless otherwise specified. For example, a plurality of steps may proceed simultaneously. For example, a plurality of steps may proceed in sequence.

[0037] Elements expressed in the singular form include the plural form as well, unless otherwise specified. For example, the term "particle" includes not only "one particle" but also "a plurality of particles (particle group)" and "an aggregate of particles (powder, powder body)".

[0038] Geometric terms (such as "parallel", "perpendicular", "orthogonal", etc.) should not be construed in a strict sense. For example, "parallel" may deviate slightly from "parallel" in the strict sense. Geometric terms may include, for example, tolerances, errors, etc. in design, operation, manufacturing, etc. The dimensional relationships in each figure may not match the actual dimensional relationships. The dimensional relationships (length, width, thickness, etc.) in each figure may be changed to assist the reader's understanding. Furthermore, some components may be omitted.

[0039] A numerical range such as "m to n%" includes the upper limit value and the lower limit value, unless otherwise specified. That is, "m to n%" indicates a numerical range of "m% or more and n% or less". Also, "m% or more and n% or less" includes "more than m% and less than n%". Furthermore, a numerically arbitrarily selected value within the numerical range may be used as a new upper limit value or lower limit value. For example, a new numerical range may be set by arbitrarily combining a numerical value within the numerical range with a numerical value described in another part of this specification, in a table, in a figure, etc.

[0040] All numerical values are modified by the term "about". The term "about" may mean, for example, ±5%, ±3%, ±1%, etc. All numerical values may be approximate values that can vary depending on the usage form of the disclosed technology. All numerical values may be expressed in significant figures. A measured value may be, unless otherwise specified, an average value in multiple measurements. The number of measurements may be 3 or more, 5 or more, or 10 or more. Generally, the reliability of the average value is expected to improve as the number of measurements increases. A measured value may be rounded off based on the number of significant figures. A measured value may include errors associated with, for example, the detection limit of the measuring device.

[0041] The stoichiometric composition formula shows representative examples of compounds. The compound may have a non-stoichiometric composition. For example, "Al2O3" is not limited to a compound having a molar ratio of "Al / O = 2 / 3". Unless otherwise specified, "Al2O3" indicates a compound containing Al and O in an arbitrary molar ratio. Further, for example, the compound may be doped with trace elements. A part of Al and O may be substituted with another element.

[0042] "Derivative" refers to a compound modified by at least one selected from the group consisting of introduction of a substituent, substitution of an atom, oxidation, reduction, and other chemical reactions in a part of the parent compound. The modified site may be one or a plurality of sites. "Substituent" includes, for example, at least one selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an unsaturated cycloalkyl group, an aromatic group, a heterocyclic group, a halogen atom (F, Cl, Br, I, etc.), an OH group, an SH group, a CN group, an SCN group, an OCN group, a nitro group, an alkoxy group, an unsaturated alkoxy group, an amino group, an alkylamino group, a dialkylamino group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an aryloxycarbonyl group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, a ureido group, a phosphoric acid amide group, a sulfo group, a carboxy group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, and a silyl group, etc. These substituents may be further substituted. When there are two or more substituents, the substituents may be the same or different. A plurality of substituents may be bonded to each other to form a ring. Note that a derivative of a polymer compound (resin material) may also be referred to as a "modified product".

[0043] "Copolymer" includes at least one selected from the group consisting of a non-designated type, a statistical type, a random type, an alternating type, a periodic type, a block type, and a graft type.

[0044] 「D50」 indicates the particle diameter at which the integration reaches 50% in the volume-based particle size distribution (cumulative distribution). The particle size distribution can be measured by the laser diffraction method.

[0045] "Recycled material" refers to all materials that can be recovered from electrodes. The recycled material is not limited to the active material. For example, the base material (e.g., Al foil, etc.) is also a recycled material. The electrode mixture is also a recycled material. The use of the recycled material is not limited to batteries. The recycled material may be used for applications other than batteries.

[0046] "Electrode" is a general term for the positive electrode, negative electrode, and bipolar electrode. That is, the electrode may be a positive electrode, a negative electrode, or a bipolar electrode. The electrode may be, for example, an electrode of a lithium-ion battery. The lithium-ion battery may be, for example, a liquid battery, a polymer battery, or an all-solid-state battery. Note that as long as the base material of the electrode contains Al, the battery is not limited to a lithium-ion battery.

[0047] "Lithium metal composite oxide" refers to a compound containing Li, a metal (other than Li), and oxygen. The lithium metal composite oxide may include, for example, layered oxides, polyanion compounds, etc.

[0048] <Manufacturing method of recycled material> Figure 1 is a schematic flowchart of the manufacturing method of the recycled material in this embodiment. Hereinafter, "the manufacturing method of the recycled material in this embodiment" may be abbreviated as "this manufacturing method". This manufacturing method includes "(a) Preparation of electrodes", "(b) Contact with aqueous ammonia", "(c) Separation", and "(d) Drying". This manufacturing method may further include, for example, "(e) Isolation of the active material" and "(f) Recycling of the active material", etc.

[0049] <(a) Preparation of electrodes> This manufacturing method includes preparing an electrode. The electrode can be obtained from any source. For example, the electrode may be recovered from within a battery by disassembling a discharged battery. The battery may be, for example, a waste product or a defective product. The reason for discarding the battery or the cause of the defect can be arbitrary. The reasons for discarding, etc. may be, for example, capacity degradation, voltage drop, micro short circuit, resistance increase, etc. For example, in the manufacturing process of the battery, an electrode discharged as a defective product may be recovered. The cause of the electrode defect can be arbitrary. The cause of the defect may be, for example, impurity mixing, basis weight defect, etc.

[0050] The electrode includes a base material and an electrode composite material. The base material can have any form. The base material may be, for example, sheet-like, plate-like, etc. The base material may include, for example, metal foil, metal porous body, etc. The base material contains Al. The base material may include, for example, pure Al foil, Al alloy foil, etc. The base material may include at least one selected from the group consisting of 1000 series materials, 2000 series materials, 3000 series materials, 4000 series materials, 5000 series materials, 6000 series materials, 7000 series materials, and 8000 series materials. For example, the "1000 series material" refers to an Al material with an alloy number in the 1000s as described in "JIS H 4000". The base material may have a thickness of, for example, 5 to 50 μm. The base material may have a single-layer structure or a multi-layer structure. For example, the base material may include a clad material. For example, a clad material may be formed by attaching a Cu foil to an Al foil.

[0051] The electrode composite material adheres to at least a part of the base material. The electrode composite material may adhere to the entire surface of the base material. The electrode composite material may adhere to a part of the surface of the base material. The electrode composite material may adhere to only one side of the base material. The electrode composite material may adhere to both the front and back surfaces of the base material. The electrode composite material may form a layer. That is, an electrode composite material layer may be formed on the surface of the base material. The electrode composite material layer may have a thickness of, for example, 10 to 1000 μm.

[0052] The electrode composite material contains an active material. The active material may contain, for example, a lithium metal composite oxide. The electrode composite material may further contain a conductive material, a binder, a solid electrolyte, etc. The active material is a particle group. The gaps between the particles serve as liquid penetration paths. The active material may have, for example, a D50 of 1 to 30 μm. Details of various materials that can be included in the electrode composite material will be described later.

[0053] <(b) Contact with aqueous ammonia> This manufacturing method includes bringing the electrode into contact with aqueous ammonia. Due to the contact between the electrode and aqueous ammonia, at least a part of the aqueous ammonia can penetrate into the interface between the electrode composite material and the base material. This is because the electrode contains a liquid penetration path. The penetration of aqueous ammonia is expected to proceed rapidly. On the surface of the base material, an ammonia complex can be formed when aqueous ammonia acts on the oxide film (anodized film). The formation of the ammonia complex can significantly reduce the adhesion between the base material and the electrode composite material.

[0054] The contact method is arbitrary. For example, the electrode may be immersed in aqueous ammonia. For example, the electrode may be put into aqueous ammonia. To promote the contact, for example, after the electrode is shredded, the electrode may be put into aqueous ammonia. To promote the contact, for example, the aqueous ammonia may be stirred.

[0055] For example, aqueous ammonia may be applied to the electrode. For example, aqueous ammonia may be applied by a roll coater or the like. For example, a sponge roll or the like may be impregnated with aqueous ammonia. Aqueous ammonia can be applied to the electrode by pressing a rotating sponge roll against the surface (electrode composite material) of the electrode. The application by a roll coater may be suitable, for example, when the electrode is in a hoop shape.

[0056] For example, aqueous ammonia may be sprayed onto the electrode. For example, aqueous ammonia may be sprayed by a spray coater or the like.

[0057] Ammonia water contains ammonia and water. Ammonia is dissolved in water. At room temperature (20 ± 5 °C), the concentration of the saturated solution is about 35%. Ammonia water may have a concentration of, for example, 0.1 to 35%. Ammonia water may have a concentration of, for example, 1 to 28%. Ammonia water in the concentration range of 1 to 28% is easy to obtain or prepare. Furthermore, in the concentration range of 1 to 28%, unfavorable reactions tend not to occur easily. Examples of unfavorable reactions include dissolution of Al, generation of H2 gas, and elution of Li. Ammonia water may contain, for example, 1 to 28% ammonia and the balance water. The balance may contain, in addition to water, for example, any additives, inevitable impurities, etc. The concentration of ammonia water may be, for example, 3% or more, 5% or more, 10% or more, 15% or more, or 20% or more. The concentration of ammonia water may be, for example, 25% or less, 20% or less, 15% or less, 10% or less, 5% or less, or 3% or less.

[0058] <(c) Separation> This manufacturing method includes separating the electrode composite material from the substrate. Due to the reduction in adhesion by contact with ammonia water, it is expected that the separation between the substrate and the electrode composite material will proceed smoothly.

[0059] The separation method is arbitrary. For example, in order to promote separation, momentum may be imparted to the electrode composite material. Momentum can be imparted by any method. For example, at least one selected from the group consisting of vibration, contact, liquid feeding, stirring, and sound waves may be imparted to the mixture (ammonia water and electrode). Here, "contact" means physically contacting an object with an object. Contact includes, for example, an operation of scraping off the electrode composite material with a scraper.

[0060] After separation, the electrode composite material and the substrate can be recovered respectively. The recovery method is arbitrary. For example, two-stage filtration may be carried out. For example, the first mixture (electrode composite material, substrate and aqueous ammonia) may be filtered by, for example, a screen filter or the like, so that the substrate may be recovered. By separating the substrate, a second mixture (electrode composite material and aqueous ammonia) is formed. The second mixture may be filtered by, for example, a cake-free filtration device or the like, so that the electrode composite material may be recovered.

[0061] The filtrate (aqueous ammonia) can be reused. That is, the filtrate may be used as aqueous ammonia in "(b) contact with aqueous ammonia". The filtrate may contain, for example, ammonium carbonate, ammonium fluoride, etc. Ammonium carbonate, ammonium fluoride, etc. may be derived from, for example, a binder, an electrolyte solution, etc. Ammonium carbonate, ammonium fluoride, etc. can also form a complex with Al. That is, ammonium carbonate, ammonium fluoride, etc. are also expected to promote the separation of the substrate and the electrode composite material.

[0062] The recovery method is not limited to filtration by a filter. For example, the electrode composite material, the substrate and aqueous ammonia may be recovered individually by a cyclone separator, a specific gravity separator, etc. By separating the substrate from the aqueous ammonia in a short time, the reaction between Al and the aqueous ammonia can be reduced. For example, the substrate may be separated from the aqueous ammonia (bulk) within 5 minutes.

[0063] <(d) Drying> This manufacturing method includes drying the electrode composite material. The drying can be carried out so that all the aqueous ammonia adhering to the electrode composite material volatilizes. By removing all the aqueous ammonia, the washing operation such as water washing can be reduced or simplified.

[0064] The drying method is optional. For example, drying may be carried out by at least one selected from the group consisting of hot air, infrared rays, and reduced pressure. The lower the drying temperature, the more expected it is to reduce the change in crystal structure. The drying temperature may be, for example, 200 °C or lower, 150 °C or lower, or 120 °C or lower. The drying temperature may be, for example, 60 °C or higher, 80 °C or higher, or 100 °C or higher. Note that the "drying temperature" indicates the maximum temperature of the workpiece during drying.

[0065] This manufacturing method may include recovering ammonia from the gas generated during drying. The recovered ammonia may be dissolved in water to regenerate aqueous ammonia. For example, high-concentration aqueous ammonia may be recovered by reflux. The concentration may be adjusted by diluting the high-concentration aqueous ammonia. The aqueous ammonia can be reused in "(b) Contact with aqueous ammonia". Reusing the aqueous ammonia is expected to reduce the processing cost.

[0066] <(e) Isolation of the active material> This manufacturing method may include separating the active material from the electrode composite material. For example, the active material may be isolated by oxidative decomposition of a binder, a conductive material, etc.

[0067] <(f) Regeneration of the active material> This manufacturing method may include regenerating the active material. In this manufacturing method, since the change in crystal structure is small, it is expected that the active material can be regenerated by a simple process. For example, Li may be supplied to the active material by heating a mixture of the active material and a lithium compound (lithium source). The lithium compound may include, for example, lithium hydroxide, lithium carbonate, etc.

[0068] <Manufacturing system> Figure 2 is a conceptual diagram showing the manufacturing system in the present embodiment. Hereinafter, the "manufacturing system in the present embodiment" may be abbreviated as the "present system". The present system 100 includes a contact device 110, a separation device 120, and a drying device 130. The present system 100 may further include, for example, a recovery device 140, a transport device (not shown), etc. Each device constituting the present system 100 may be separately independent. In the present system 100, a plurality of devices may be integrated to form one device.

[0069] The contact device 110 brings the electrode 10 into contact with the aqueous ammonia 20. The contact device 110 may include, for example, a liquid tank and a stirring device, etc. The liquid tank stores the aqueous ammonia 20. The stirring device stirs the aqueous ammonia 20. The contact device 110 may include, for example, a coating device, etc. The contact device 110 may include, for example, a roll coater, a spray coater, etc.

[0070] The separation device 120 separates the electrode composite 12 from the substrate 11 after the contact between the electrode 10 and the aqueous ammonia 20. The separation device 120 may include, for example, a screen filter, a disk filter, a rotary filter, a doctor blade, a scraper, a cyclone separator, a specific gravity separator, etc.

[0071] The drying device 130 dries the electrode composite 12 after the separation of the substrate 11 and the electrode composite 12. The drying device 130 may include, for example, a hot air drying device, an infrared drying device, a vacuum device, etc.

[0072] The recovery device 140 recovers ammonia from the gas generated in the drying device 130. The recovery device 140 may include, for example, a reflux device, etc. The recovery device 140 may prepare aqueous ammonia from the recovered ammonia. The recovery device 140 may include a circulation device, etc. The circulation device may supply the aqueous ammonia to the contact device 110.

[0073] The transfer device can transfer the workpiece between each device. The transfer device may transfer the workpiece, for example, by a roll-to-roll method.

[0074] <First System> Figure 3 is a conceptual diagram showing the first system. This system 100 (see Figure 2) may include a first system 101. The first system 101 includes a liquid tank 111, a stirring device 112, a screen filter 121, and a filtering device 122. The liquid tank 111 and the stirring device 112 constitute a contact device 110 (see Figure 2). The screen filter 121 and the filtering device 122 constitute a separation device 120 (see Figure 2).

[0075] The first system 101 can operate as follows. For example, the electrode 10 may be recovered by disassembling a discharged battery. The electrode 10 includes a base material 11 and an electrode composite material 12.

[0076] Ammonia water 20 is stored in the liquid tank 111. When the electrode 10 is immersed in the ammonia water 20 in the liquid tank 111, the electrode 10 comes into contact with the ammonia water 20. By the stirring device 112 stirring the mixture, the penetration of the ammonia water 20 (contact with the base material 11) is promoted. Furthermore, the stirring device 112 can impart momentum to the workpiece. By the stirring device 112 stirring the mixture, the peeling of the electrode composite material 12 can also be promoted. The peeled electrode composite material 12 may be pulverized in the liquid. When the refined electrode composite material 12 is dispersed in the liquid, a slurry may be formed.

[0077] After the electrode composite material 12 is peeled from the base material 11, the screen filter 121 can separate the base material 11. Furthermore, the filtering device 122 can separate the electrode composite material 12. The filtering device 122 may be, for example, a total amount filtration method or a cross-flow filtration method. When the electrode composite material 12 is dried by a drying device (not shown), the ammonia water can be volatilized in its entirety.

[0078] <Second System> Figure 4 is a conceptual diagram showing the second system. This system 100 (see Figure 2) may include a second system 102. The second system 102 includes an application device 113, a peeling device 123, and a winding device.

[0079] The second system 102 may operate as follows. For example, in the battery manufacturing process, the electrode 10 discharged as a defective product is recovered. The electrode 10 forms a hoop. The electrode 10 may be wound around a bobbin, for example.

[0080] The winding device corresponds to a conveying device. The winding device conveys the workpiece. The winding device can impart momentum to the workpiece. The winding device includes a delivery roll 151, a first touch roll 152, a second touch roll 153, and a winding roll 154. The delivery roll 151 feeds out the electrode 10, and the winding roll 154 winds up the base material 11. Power may be applied to both the delivery roll 151 and the winding roll 154. Power may be applied only to the winding roll 154. The first touch roll 152 and the second touch roll 153 can adjust the difference in tension between the delivery side and the winding side.

[0081] The application device 113 constitutes a contact device 110 (see Figure 2). The application device 113 may include, for example, a sponge roll and a fountain. Ammonia water is impregnated into the sponge roll. The fountain can supply ammonia water to the sponge roll so that the impregnation amount of ammonia water in the sponge roll is maintained within a certain range. When the sponge roll contacts the electrode 10, ammonia water is applied to the surface of the electrode 10. A pair of sponge rolls may apply ammonia water to both the front and back surfaces of the electrode 10 simultaneously.

[0082] The peeling device 123 constitutes the separation device 120 (see FIG. 2). The peeling device 123 may include, for example, a doctor blade or the like. The peeling device 123 can peel the electrode composite material 12 by contact (external force). For example, a pair of doctor blades may scrape off the electrode composite materials 12 on both the front and back surfaces simultaneously. After scraping off, the electrode composite material 12 can be dried by a drying device (not shown). By drying, all of the aqueous ammonia can volatilize. After the peeling of the electrode composite material 12, the base material 11 can be recovered by the winding roll 154.

[0083] <Electrode composite material> Hereinafter, the details of various materials that may be included in the electrode composite material will be described. The electrode material may include, for example, a binder in a mass fraction of 0.1 to 10%, a conductive material of 0 to 10%, and the balance being the active material. The balance may include, in addition to the active material, a solid electrolyte, various additives, inevitable impurities, etc. The solid electrolyte may include, for example, Li, sulfur, phosphorus, etc.

[0084] <Active material> The active material causes an electrode reaction. The active material may be a positive electrode active material or a negative electrode active material. The electrode composite material may contain one type of active material alone or may contain a plurality of types of active materials. The active material may include, for example, a lithium metal composite oxide. The lithium metal composite oxide may have an arbitrary crystal structure.

[0085] The lithium metal composite oxide may include, for example, a crystal structure belonging to the space group R-3m. For example, a compound represented by the general formula "LiMO2" may have a crystal structure belonging to the space group R-3m. The lithium metal composite oxide may have, for example, the composition of the following formula (1).

[0086] Li 1-a Ni x M 1-x O2…(1) In the formula, the relationship of -0.5 ≦ a ≦ 0.5, 0 ≦ x ≦ 1 is satisfied. M may include, for example, at least one selected from the group consisting of Co, Mn, and Al.

[0087] In the above formula (1), for example, the relationships of 0 < x ≤ 0.1, 0.1 ≤ x ≤ 0.2, 0.2 ≤ x ≤ 0.3, 0.3 ≤ x ≤ 0.4, 0.4 ≤ x ≤ 0.5, 0.5 ≤ x ≤ 0.6, 0.6 ≤ x ≤ 0.7, 0.7 ≤ x ≤ 0.8, 0.8 ≤ x ≤ 0.9, or 0.9 ≤ x ≤ 1 may be satisfied. For example, the relationships of -0.4 ≤ a ≤ 0.4, -0.3 ≤ a ≤ 0.3, -0.2 ≤ a ≤ 0.2, or -0.1 ≤ a ≤ 0.1 may be satisfied.

[0088] LiMO2 may include, for example, at least one selected from the group consisting of LiCoO2, LiMnO2, LiNi 0.9 Co 0.1 O2, LiNi 0.9 Mn 0.1 O2, and LiNiO2.

[0089] The lithium metal composite oxide may have, for example, the composition of the following formula (2). A compound having the composition of the following formula (2) may also be referred to as "NCM".

[0090] Li 1-a Ni x Co y Mn z O2…(2) In the formula, the relationships of -0.5 ≤ a ≤ 0.5, 0 < x < 1, 0 < y < 1, 0 < z < 1, and x + y + z = 1 are satisfied.

[0091] In the above formula (2), for example, the relationships of 0 < x ≤ 0.1, 0.1 ≤ x ≤ 0.2, 0.2 ≤ x ≤ 0.3, 0.3 ≤ x ≤ 0.4, 0.4 ≤ x ≤ 0.5, 0.5 ≤ x ≤ 0.6, 0.6 ≤ x ≤ 0.7, 0.7 ≤ x ≤ 0.8, 0.8 ≤ x ≤ 0.9, or 0.9 ≤ x < 1 may be satisfied.

[0092] In the above formula (2), for example, the relationship of 0 < y ≤ 0.1, 0.1 ≤ y ≤ 0.2, 0.2 ≤ y ≤ 0.3, 0.3 ≤ y ≤ 0.4, 0.4 ≤ y ≤ 0.5, 0.5 ≤ y ≤ 0.6, 0.6 ≤ y ≤ 0.7, 0.7 ≤ y ≤ 0.8, 0.8 ≤ y ≤ 0.9, or 0.9 ≤ y < 1 may be satisfied.

[0093] In the above formula (2), for example, the relationship of 0 < z ≤ 0.1, 0.1 ≤ z ≤ 0.2, 0.2 ≤ z ≤ 0.3, 0.3 ≤ z ≤ 0.4, 0.4 ≤ z ≤ 0.5, 0.5 ≤ z ≤ 0.6, 0.6 ≤ z ≤ 0.7, 0.7 ≤ z ≤ 0.8, 0.8 ≤ z ≤ 0.9, or 0.9 ≤ z < 1 may be satisfied.

[0094] NCM is, for example, LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2, LiNi 0.4 Co 0.3 Mn 0.3 O2, LiNi 0.3 Co 0.4 Mn 0.3 O2, LiNi 0.3 Co 0.3 Mn 0.4 O2, LiNi 0.5 Co 0.2 Mn 0.3 O2, LiNi 0.5 Co 0.3 Mn 0.2 O2, LiNi 0.5 Co 0.4 Mn 0.1 O2, LiNi 0.5 Co 0.1 Mn 0.4 O2, LiNi 0.6 Co 0.2 Mn 0.2 O2, LiNi 0.6 Co 0.3 Mn 0.1 O2, LiNi 0.6 Co 0.1 Mn 0.3 O2, LiNi 0.7 Co 0.1 Mn 0.2 O2, LiNi 0.7 Co 0.2 Mn 0.1 O2, LiNi0.8 Co 0.1 Mn 0.1 O2, and LiNi 0.9 Co 0.05 Mn 0.05 may contain at least one selected from the group consisting of O2.

[0095] The lithium metal composite oxide may have, for example, the composition of the following formula (3). A compound having the composition of the following formula (3) may also be referred to as "NCA".

[0096] Li 1-a Ni x Co y Al z O2…(3) In the formula, the relationships of -0.5 ≦ a ≦ 0.5, 0 < x < 1, 0 < y < 1, 0 < z < 1, and x + y + z = 1 are satisfied.

[0097] In the above formula (3), for example, the relationships of 0 < x ≦ 0.1, 0.1 ≦ x ≦ 0.2, 0.2 ≦ x ≦ 0.3, 0.3 ≦ x ≦ 0.4, 0.4 ≦ x ≦ 0.5, 0.5 ≦ x ≦ 0.6, 0.6 ≦ x ≦ 0.7, 0.7 ≦ x ≦ 0.8, 0.8 ≦ x ≦ 0.9, or 0.9 ≦ x < 1 may be satisfied.

[0098] In the above formula (3), for example, the relationships of 0 < y ≦ 0.1, 0.1 ≦ y ≦ 0.2, 0.2 ≦ y ≦ 0.3, 0.3 ≦ y ≦ 0.4, 0.4 ≦ y ≦ 0.5, 0.5 ≦ y ≦ 0.6, 0.6 ≦ y ≦ 0.7, 0.7 ≦ y ≦ 0.8, 0.8 ≦ y ≦ 0.9, or 0.9 ≦ y < 1 may be satisfied.

[0099] In the above formula (3), for example, the relationships of 0 < z ≦ 0.1, 0.1 ≦ z ≦ 0.2, 0.2 ≦ z ≦ 0.3, 0.3 ≦ z ≦ 0.4, 0.4 ≦ z ≦ 0.5, 0.5 ≦ z ≦ 0.6, 0.6 ≦ z ≦ 0.7, 0.7 ≦ z ≦ 0.8, 0.8 ≦ z ≦ 0.9, or 0.9 ≦ z < 1 may be satisfied.

[0100] NCA is, for example, LiNi 0.7 Co 0.1 Al 0.2 O2, LiNi0.7 Co 0.2 Al 0.1 O2, LiNi 0.8 Co 0.1 Al 0.1 O2, LiNi 0.8 Co 0.17 Al 0.03 O2, LiNi 0.8 Co 0.15 Al 0.05 O2, and LiNi 0.9 Co 0.05 Al 0.05 It may contain at least one selected from the group consisting of O2.

[0101] The lithium metal composite oxide may include, for example, a crystal structure belonging to the space group C2 / m. The lithium metal composite oxide may have, for example, a composition represented by the following formula (4).

[0102] Li2MO3…(4) In the formula, M may include at least one selected from the group consisting of, for example, Ni, Co, Mn, and Fe.

[0103] The lithium metal composite oxide may include, for example, a crystal structure belonging to the space group Fd-3m. The lithium metal composite oxide may have, for example, a composition represented by the following formula (5) or the following formula (6).

[0104] LiMn 2-x M x O4…(5) In the formula, the relationship 0 ≦ x ≦ 2 is satisfied. M may include at least one selected from the group consisting of, for example, Ni, Fe, and Zn.

[0105] Li 4+x Ti5O 12 …(6) In the formula, the relationship -1 ≦ x ≦ 3 is satisfied.

[0106] The lithium metal composite oxide may contain, for example, a polyanion compound. The polyanion compound may contain, for example, phosphates (such as LiFePO4, etc.), silicates, borates, etc. The polyanion compound may have a composition of, for example, the following formula (7), the following formula (8), the following formula (9), or the following formula (10).

[0107] LiMPO4…(7) Li 2-x MPO4F …(8) Li2MSiO4…(9) LiMBO3…(10) In the above formulas (7) to (10), M may contain at least one selected from the group consisting of, for example, Fe, Mn, and Co. In the above formula (8), for example, the relationship of 0≦x≦2 may be satisfied.

[0108] A dopant may be added to the lithium metal composite oxide. The dopant may be diffused throughout the particles or may be locally distributed. For example, the dopant may be unevenly distributed on the particle surface. The dopant may be a substitutional solid solution atom or an interstitial solid solution atom. The addition amount of the dopant (mole fraction with respect to the entire active material) may be, for example, 0.01 to 5%, 0.1 to 3%, or 0.1 to 1%. One type of dopant may be added, or two or more types of dopants may be added. Two or more types of dopants may form a complex.

[0109] The dopant may contain at least one selected from the group consisting of, for example, B, C, N, halogen, Si, Na, Mg, Al, Mn, Co, Cr, Sc, Ti, V, Cu, Zn, Ga, Ge, Se, Sr, Y, Zr, Nb, Mo, In, Pb, Bi, Sb, Sn, W, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and actinoids.

[0110] <Conductive material> The conductive material can form an electron conduction path within the electrode composite material. The conductive material can contain any component. The conductive material may include, for example, at least one selected from the group consisting of graphite, acetylene black (AB), Ketjen black (registered trademark), vapor-grown carbon fiber (VGCF), carbon nanotube (CNT), and graphene flake (GF).

[0111] <Binder> The binder can fix the electrode composite material to the substrate. The binder can contain any component. The binder may include, for example, at least one selected from the group consisting of polyvinylidene fluoride (PVdF), vinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), alginic acid, polyacrylic acid (PAA), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyoxyethylene alkyl ether, styrene butadiene rubber (SBR), acrylate butadiene rubber (ABR), acrylic resin, methacrylic resin, and derivatives thereof.

Explanation of Reference Numerals

[0112] 10 Electrode, 11 Substrate, 12 Electrode Composite Material, 20 Ammonia Water, 100 Main System, 101 First System, 102 Second System, 110 Contact Device, 111 Liquid Tank, 112 Stirring Device, 113 Coating Device, 120 Separation Device, 121 Screen Filter, 122 Filtration Device, 123 Peeling Device, 130 Drying Device, 140 Recovery Device, 151 Feed Roll, 152 First Touch Roll, 153 Second Touch Roll, 154 Take-up Roll.

Claims

1. (a) preparing an electrode including a substrate and an electrode composite material; (b) bringing the electrode into contact with aqueous ammonia; (c) separating the electrode composite material from the substrate; and (d) drying the electrode composite material, in this order, in the above (a), the electrode composite material is attached to at least a part of the substrate, the substrate contains aluminum, the electrode composite material contains an active material, and the above (d) includes recovering ammonia from the gas generated during drying, A method for manufacturing a recycled material.

2. The aqueous ammonia contains ammonia at a mass fraction of 1 to 28%, The method for manufacturing a recycled material according to Claim 1.

3. The active material contains a lithium metal composite oxide, The method for manufacturing a recycled material according to Claim 1.

4. The above (b) includes immersing the electrode in the aqueous ammonia, The method for manufacturing a recycled material according to any one of Claims 1 to 3.

5. The above (b) includes applying the aqueous ammonia to the electrode, The method for manufacturing a recycled material according to any one of Claims 1 to 3.

6. The above (b) includes spraying the aqueous ammonia onto the electrode, The method for manufacturing a recycled material according to any one of Claims 1 to 3.

7. The above (c) includes imparting momentum to the electrode composite material, The method for manufacturing a recycled material according to any one of Claims 1 to 3.

8. The electrode prepared in (a) forms a hoop, and further includes conveying the electrode in a roll-to-roll manner at least between (b) and (c). The method for manufacturing a recycled material according to any one of Claims 1 to 3.

9. (e) Separating the active material from the electrode composite, and (f) Recycling the active material, further including these in this order. The method for manufacturing a recycled material according to any one of Claims 1 to 3.

10. A manufacturing system for manufacturing a recycled material from an electrode including a substrate and an electrode composite, including a contact device, a separation device, a drying device, and a recovery device, the contact device is configured to bring the electrode into contact with aqueous ammonia, the separation device is configured to separate the electrode composite from the substrate after contact between the electrode and the aqueous ammonia, the drying device is configured to dry the electrode composite after separation of the substrate and the electrode composite, and the recovery device is configured to recover ammonia from the gas generated in the drying device. The manufacturing system.

11. Further including a conveying device, and the conveying device is configured to convey the electrode in a roll-to-roll manner at least between the contact device and the separation device. The manufacturing system according to Claim 10.

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