Battery recycling equipment and method

Abstract

The invention relates to a method and an apparatus (100) for recycling waste batteries, the apparatus comprising:-first comminution means (110) for comminuting waste batteries to a first degree of comminution in order to obtain comminuted battery material; -a drying device (120) arranged downstream of the first comminution device (110) for drying the comminuted battery material; -a second comminution device (130), which is designed to be explosion-proof and is arranged downstream of the drying device (120), for comminution of the dried battery material to a second degree of comminution, which is greater than the first degree of comminution; and-a pyrolysis device (140) arranged downstream of the second comminution device (130) for pyrolyzing the dried and comminuted battery material.

Description

Technical Field

[0001] The present disclosure relates to an apparatus for recycling waste batteries, particularly lithium-ion batteries, and to a method for recovering valuable materials from waste batteries. Background Art

[0002] Lithium-ion battery materials are a complex mixture of various elements and compounds. For example, many lithium-ion battery materials contain valuable metals such as lithium, aluminum, copper, nickel, cobalt, and / or manganese. This active battery material is coated on a metal foil (such as aluminum (Al) foil) with an adhesive to form a corresponding battery cathode. It may be desirable to recover various elements and compounds from the lithium-ion battery materials of the discarded battery cathode. For example, it may be advantageous to recover lithium, aluminum, copper, nickel, cobalt, and / or manganese. Accordingly, there is a need for devices and methods for recycling waste batteries.

[0003] DE 10 2015 207 843 A1 discloses a recycling apparatus for waste batteries. The batteries are pretreated, particularly discharged and disassembled, in a complex manner before being shredded and dried. This increases the operating costs of the apparatus, especially because labor is required.

[0004] EP 2 975 686 B1 relates to a method for recycling the cathode material of a lithium-ion battery, the method comprising: (i) providing a lithium-ion battery cathode comprising a metal foil coated with a cathode material; (ii) grinding the cathode in an impact mill to provide a granular cathode comprising metal foil particles having an average particle size of at least 200 μm and cathode material particles having an average particle size less than 200 μm; (iii) filtering the granular cathode from the impact mill in a dust collector; (iv) separating the cathode material particles from the granular cathode to provide a recycled cathode material.

[0005] CN 111 495 925A describes a method for pyrolysis, defluorination, and dechlorination of waste lithium batteries, the method comprising the steps of: discharging and disassembling the waste lithium batteries; performing primary crushing, drying the crushed product, performing primary separation on the dried crushed product, performing secondary crushing and secondary separation, performing pyrolysis, defluorination, dechlorination, and in-situ fluorine and chlorine absorption on the separated material, and spreading and screening the pyrolyzed product to obtain a black powder.

[0006] WO 2017 / 102810 A1 relates to a method for producing a comminuted dry material from a raw material, the method comprising the steps of: (a) providing heated drying gas from a drying gas source; (b) providing the raw material in a storage bin; (c) feeding the raw material and the heated drying gas into a comminution device; (d) comminuting and drying the raw material within the comminution device to obtain a comminuted dry material; (e) collecting a mixture of the drying gas and the comminuted dry material from the comminution device and feeding the mixture into a separator to separate the comminuted dry material from the drying gas; wherein the method further comprises the steps of: (f) recycling at least a portion of the drying gas from step (e) as preconditioning gas and feeding the preconditioning gas into a lower portion of the storage bin to precondition the raw material.

[0007] US2021 / 359312 A1 relates to a device for recycling waste batteries, the device comprising: a comminution device for comminuting waste batteries in a comminution space; a drying device arranged downstream of the comminution device for drying the comminuted batteries; an intermediate storage device arranged between the comminution device and the drying device. The device comprises respective inert gas supply lines for each of the comminution space of the comminution device, the intermediate storage space of the intermediate storage device, and the drying space of the drying device.

[0008] EP 3 641 036 A1 relates to a device for recycling waste batteries, the device comprising a comminution device for comminuting waste batteries in a comminution space. The device comprises a drying device arranged downstream of the comminution device for drying the comminuted batteries. The device comprises an intermediate storage device arranged between the comminution device and the drying device. The device comprises a stirring device for keeping the comminuted batteries received in the intermediate storage space in motion. The device comprises respective inert gas supply lines for each of the comminution space of the comminution device, the intermediate storage space of the intermediate storage device, and the drying space of the drying device.

[0009] The object of the present disclosure is to provide an improved device for recycling waste batteries and an improved method for recycling waste batteries. Summary of the Invention

[0010] Provided is a device for recycling waste batteries, which provides a first crushing of the waste batteries before drying the waste batteries and a second crushing of the waste batteries after drying the waste batteries. The device includes a first crushing device, which is used to crush the waste batteries to a first crushing degree in a first crushing space to obtain crushed battery materials. The device includes a drying device, which is arranged downstream of the first crushing device and is used to dry the crushed battery materials. The device includes a second crushing device, which is arranged downstream of the drying device and is configured to further crush the dried battery materials to a second crushing degree in a second crushing space, and the second crushing degree is greater than the first crushing degree. The device further includes at least one separation device, which is used to separate the battery material particles of the crushed battery materials with different particle sizes or particle size ranges from each other, that is, to separate the battery material particles with different particle sizes or particle size ranges into two or more particle parts with correspondingly two or more different particle size ranges, for example, to separate the battery material particle part with a small particle size from the battery material particle part with a large particle size.

[0011] The device further includes a pyrolysis device, which is arranged downstream of the second crushing device and the at least one separation device and includes a pyrolysis space.

[0012] At least the second crushing device is designed to be explosion-proof, that is, explosion-protected, that is, to protect against possible explosions. In some embodiments, in addition to the second crushing device, one or more of the other components of the device (such as the first crushing device, the drying device, one or more of the at least one separation device, and / or the pyrolysis device) are also explosion-proof.

[0013] Also provided is a method for recycling waste batteries, which includes: using a first crushing device to crush the waste batteries to a first crushing degree to obtain crushed battery materials, drying the crushed battery materials, using a second crushing device to crush the crushed and dried battery materials to a second crushing degree, and pyrolyzing the crushed and dried battery materials at a temperature in the range of 400°C to 600°C, for example.

[0014] The present invention is based on the following recognition: By crushing the waste batteries before and after drying the waste batteries as proposed, the active battery materials can be effectively separated from the metal foils (such as aluminum foils) with a yield of at least 95% (such as 99%), because the metal foil particles and the active battery material particles of the crushed battery materials have significantly different average particle sizes, making it possible to effectively separate these particles from each other (such as by screening).

[0015] In some embodiments, the first shredding device has provided a two-step shredding of waste batteries using a primary shredder and a downstream secondary shredder before drying. The primary shredder feeds battery material particles with a maximum diameter size of 50 mm, i.e., battery material particles that can pass through a 50 mm sieve size, while the secondary shredder feeds battery material particles with a maximum diameter size of 20 mm, i.e., battery material particles that can pass through a 20 mm sieve size.

[0016] In some embodiments, the device includes an intermediate storage device disposed between the first shredding device and the drying device. The intermediate storage device further includes a stirring device that is designed and intended to keep the shredded battery material received in the intermediate storage space in motion.

[0017] In some embodiments, the device includes a plurality of separation devices. In some embodiments, at least one first separation device is disposed between the first shredding device and the drying device, and / or at least one second separation device is disposed between the drying device and the second shredding device, and / or at least one third separation device is disposed between the second shredding device and the pyrolysis device.

[0018] The at least one first separation device is used to pre-sort the battery material particles of the shredded battery material, i.e., split the battery material with the at least one first separation device to prevent oversized battery material particles in the shredded battery from being fed to the drying device.

[0019] The at least one second separation device is used to pre-sort the battery material particles of the shredded and dried battery material, i.e., split the shredded and dried battery material with the at least one second separation device. Thereby, coarse battery material particles of Al and steel (Fe), plastics, foils, etc. are removed, and undersized battery material is left. Within the scope of the present disclosure, the term "undersized battery material" should be understood as battery material of waste batteries that is configured to pass through the corresponding separation device due to its particle size.

[0020] In some embodiments, a plurality of second separation devices (such as sieves, sieve screens, zz sieves) that can be connected in series are used to remove coarser battery material particles of Al and steel (Fe), plastics, foils, etc. The undersized battery material can be discharged from each of the second separation devices connected in series and directly transferred to the pyrolysis device as a first black material portion or transferred to the second shredding device.

[0021] At least a portion of the undersized battery material is fed to the second shredding device. In some embodiments, the remaining portion of the undersized battery material is directly fed to the pyrolysis device.

[0022] The at least one third separation device is used to sort battery material particles from the second comminution device, i.e., to split the battery material comminuted by the second comminution device with the at least one third separation device. The battery material that is too small in size to pass through the third separation device is fed to the pyrolysis device. In some embodiments, the third separation device is configured to separate battery material particles within a desired size range for direct transfer to the pyrolysis device as a second black mass portion.

[0023] In some embodiments, the apparatus includes a dust collector. In some embodiments, the dust collector is coupled to at least one of the second comminution device and / or at least one of the at least one separation device, the dust collector includes a blower, a dust filter, and a dust receiver, and is configured to remove / extract the dust-laden air from the second comminution device and / or the corresponding separation device. Thanks to the dust collector, the safety of the recycling method can be improved. In some embodiments, the dried and comminuted battery material is removed from the second comminution device and filtered in the dust collector. The removal of the dried and comminuted battery material is achieved by a sieve acting as the third separation device, which is arranged downstream of the second comminution device and is configured to further separate battery material particles within a desired size range for transfer to the dust collector. These battery material particles are transferred to the dust collector by using a blower so that no dust can escape into the ambient air. These battery material particles are collected in the dust filter and can be fed to the pyrolysis device as a third black mass portion. In some embodiments, the battery material particles accumulated in the dust filter can be directly transferred to the pyrolysis device or transferred to the pyrolysis device via an additional separation device.

[0024] In some embodiments, the dust collector is coupled to a second separation device arranged between the drying device and the second comminution device. The second separation device is configured to allow only battery material particles within a desired size range to pass through for transfer to the dust collector. These battery material particles are also collected in the dust filter and can be fed to the pyrolysis device as a black mass.

[0025] In some embodiments, the at least one second separation device and / or the at least one third separation device includes a plurality of sieves. These sieves in the plurality of sieves can be arranged in series, and each sieve is configured to remove particles whose size belongs to a specific size range of the sieve. The plurality of sieves is configured to be supplied with battery material particles discharged from the drying device and / or the second comminution device. Depending on the desired degree of splitting, the number of screening fractions to be provided can be set.

[0026] In some embodiments, the device includes corresponding inert gas supply pipelines for some or each of the first crushing space for the first crushing device, the intermediate storage space for the intermediate storage device, the drying space for the drying device, the second crushing space for the second crushing device, and the pyrolysis space for the pyrolysis device. Supplying inert gas can achieve the purpose of explosion prevention. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is a schematic diagram of an exemplary recycling device according to the present disclosure.

[0028] Figure 2 is a schematic diagram of an exemplary second crushing device that is part of an exemplary recycling device according to the present disclosure.

[0029] DEFINITIONS

[0030] In the present disclosure, the term "battery" encompasses not only non-rechargeable primary batteries but also storage batteries, i.e., rechargeable energy storage batteries. In particular, the devices of the present disclosure are suitable for processing rechargeable and non-rechargeable storage batteries that contain lithium, especially lithium compounds and / or lithium ions, and are very generally referred to herein as "lithium batteries".

[0031] Furthermore, in the present disclosure, the term "drying" is also used to remove, especially evaporate electrolytes such as dimethyl carbonate (DMC), diethyl carbonate (DEC), and / or ethyl methyl carbonate (EMC). Although it involves not only the removal of liquid substances but also the removal of solids, the term "drying" has become common in the technical language used for this purpose.

[0032] The term "crushing" is used herein to describe any mechanical treatment of waste batteries in or by any suitable crushing device, especially by shredders and / or mills such as ball mills, preferably jet mills, impact mills, especially rotor impact mills.

[0033] The term "separation device" is used herein for any type of device suitable for separating battery material particles into different parts. Thus, the separation device can be, for example, a screening device, a sieving device, and / or any combination thereof.

[0034] DETAILED DESCRIPTION

[0035] There is provided a device for recycling waste batteries, the device comprising a first crushing device for crushing waste batteries to a first degree in a first crushing space. The device comprises a drying device arranged downstream of the first crushing device for drying the crushed batteries to obtain dried battery material. The device comprises: a second crushing device for crushing the dried battery material to a second degree in a second crushing space; and a pyrolysis device for pyrolyzing the crushed and dried battery material.

[0036] In some embodiments, the device comprises an intermediate storage device arranged between the first crushing device and the drying device. The intermediate storage device further comprises a stirring device designed and intended to keep the crushed battery material received in the intermediate storage space in motion.

[0037] In some embodiments, some or all of the components of the device that are subject to the risk of explosion (such as the first crushing device and / or the second crushing device, the drying device, the intermediate device, and / or the separation device) are designed to be explosion-proof. According to the invention, at least the second crushing device is designed to be explosion-proof.

[0038] Hereinafter, some measures for achieving explosion protection according to the invention are proposed for use and / or taken individually and / or in combination.

[0039] To reduce the risk of ignition and / or spontaneous combustion, in some embodiments, an inert gas is supplied to at least some of the first crushing device, the intermediate storage device, the drying device, the second crushing device, and at least one separation device, such that the corresponding device / component is explosion-proof. The inert gas is a gas that at least counteracts (if not even prevents) the ignition and / or spontaneous combustion of the crushed battery material during an electrochemical reaction. For example, nitrogen and / or carbon dioxide gas can be used as the inert gas. The inert gas sufficiently reduces the concentration of oxygen. Thus, explosion protection can be achieved. By inerting with the inert gas, an air cushion is formed in the potential explosion area of the corresponding device / component of the device, thereby preventing the formation of an explosive atmosphere.

[0040] In some embodiments, explosion-proof means being able to withstand a pressure exceeding atmospheric pressure (i.e., higher than ambient pressure) by 10 bar, especially in the case of a dust explosion hazard.

[0041] In some embodiments, "designed to be explosion-proof" means that the corresponding component (e.g., the first comminution device, the intermediate storage device, the drying device, the second comminution device, and / or the at least one separation device) is structurally (mechanically) designed to withstand a pressure up to 10 bar above ambient pressure, i.e., to tolerate a pressure up to 10 bar above ambient pressure. For example, the corresponding component is strengthened in its corresponding construction, e.g., having a strengthened wall thickness.

[0042] Regarding the mechanical design of the components of the device that are potentially affected by an explosion (i.e., at least the second comminution device), some embodiments provide strengthening of the corresponding components by a larger wall thickness of the corresponding components (e.g., the walls of the first comminution device, the intermediate storage device, the drying device, the second comminution device, and / or the at least one separation device) and / or thicker bolts / screws and nuts that prevent the walls of the corresponding components from rupturing, such that they can withstand a larger pressure, e.g., a pressure up to 10 bar above atmospheric pressure in the presence of a dust explosion hazard. Thus, the corresponding components (e.g., the first comminution device, the intermediate storage device, the drying device, the second comminution device, and / or the at least one separation device) are designed to be shock-resistant and thus explosion-proof. Depending on the corresponding dimensions of the corresponding components, the walls of the corresponding components and the means provided for their joining (i.e., for their design-related connection to other components), such as bolts, nuts, etc., are selected to be appropriately stable in order to withstand the pressure generated in the event of a possible explosion in a calculable or evaluable manner. The described constructive (structural) explosion protection includes strengthening of the components or structures of the device that are expected to be potentially exposed to the explosion pressure and / or flying parts inside the device. As mentioned, this can involve, for example, the first comminution device, the intermediate storage device, the drying device, the second comminution device, and / or the at least one separation device.

[0043] To achieve explosion protection of the second comminution device, i.e., to design the second comminution device to be explosion-proof, in some embodiments, the second comminution device is constructed completely or partially in accordance with the standard DIN EN 13445-3:2021. This means that, to be explosion-proof, the second comminution device is constructed completely or partially in accordance with the standard DIN EN 13445-3:2021, i.e., the second comminution device is explosion-proof by virtue of its structural design in accordance with the standard DIN EN 13445-3:2021.

[0044] In the context of the present disclosure, in some embodiments, the standard DIN EN 13445-3:2021 is also used as a reference to future versions of the standard DIN EN 13445-3:2021, in which case the reference to the corresponding subchapters within the also-mentioned standard DIN EN 13445-3:2021 may need to be adjusted.

[0045] In some embodiments, the second comminution device is an impact mill. In some embodiments, the second comminution device is a rotor impact mill.

[0046] Accordingly, in some embodiments, when an impact mill (such as a rotor impact mill) is used as the second comminution device, the mill housing and / or the grinding chamber of the impact mill are designed to have an explosion protection of up to 10 bar above atmospheric pressure. For this purpose, the impact mill, i.e., at least the mill housing and / or the grinding chamber of the impact mill, is constructed in accordance with the standard DIN EN 13445-3:2021. Accordingly, the thickness of the wall of the impact mill, i.e., at least the thickness of the generally flat rear wall of the grinding chamber of the impact mill, is approximately proportional to the square root of the equivalent diameter of the rear wall of the grinding chamber multiplied by the maximum expected pressure inside the impact mill, more precisely to the square root of the equivalent diameter of the rear wall of the grinding chamber multiplied by the quotient of the maximum expected pressure inside the impact mill and the existing / allowed tensile stress in the construction material of the impact mill (i.e., in the construction material of the grinding chamber). The calculation method for calculating the equivalent diameter (such as the equivalent diameter of the rear wall) is well known to those skilled in the art. The maximum expected pressure of at least the second comminution device (such as an impact mill as the second comminution device, such as a rotor impact mill) is designed to have an explosion protection of 10 bar above atmospheric pressure. For explosion protection, the required minimum thickness of the rear wall of the grinding chamber of the impact mill can be determined or defined as follows (see Chapter 10.4.3 of DIN EN 13445-3:2021):

[0047]

[0048] where d min is the minimum thickness of the rear wall, C1 is a proportionality coefficient, D is the equivalent diameter of the rear wall, p is the maximum expected pressure inside the impact mill, and f is the existing / allowed tensile stress in the construction material of the impact mill (i.e., in the construction material of the grinding chamber). The allowed tensile stress depends on the material used to manufacture the wall, i.e., the steel used. For example, for VA steel (i.e., stainless steel), the allowed tensile stress can be in the range of 500 N / mm 2 of.

[0049] In some embodiments, the wall in question is a substantially flat panel. In addition, the substantially flat panel has a substantially constant thickness, i.e., within a given allowable tolerance.

[0050] In some embodiments, the wall thickness of the cylindrical wall is also provided in accordance with the standard DIN EN 13445-3:2021 (see, for example, Chapter 7.4 of DIN EN 13445-3:2021).

[0051] In some embodiments, wall connections / wall joints that must be provided and may be subject to increased pressure due to the design of the equipment (such as an impact mill) are selected as welded and / or screwed connections.

[0052] In some embodiments, the screws to be used for this purpose are also designed to be explosion-proof. For example, the diameter of the screw is selected to be proportional to the square root of the tensile stress that will occur in the screw when the maximum allowable pressure is applied to the equipment (such as an impact mill, for example, the mill housing or the grinding chamber). As described above, the maximum allowable dominant pressure inside the equipment (such as an impact mill) is at most 10 bar above atmospheric pressure. How to arrange the screws for this purpose is further described in Roloff / Matek, Maschinenelemente, Vieweg& Verlagsgesellschaft, Braunschweig, 7. Auflage, 1976.

[0053] The above-described explosion-proof measures are described here as an example for the second comminution device, but can also be applied in a similar manner to other components of the equipment. In some embodiments, in addition to the second comminution device, other components of the equipment that may be affected by a possible explosion (such as the first comminution device, the intermediate storage device, the drying device, and / or the at least one separation device) are also designed (constructed) completely or partially in accordance with the standard DIN EN 13445-3:2021. This means that the corresponding components (such as the first comminution device, the intermediate storage device, the drying device, and / or the at least one separation device) are explosion-proof due to their structural design in accordance with the standard DIN EN 13445-3:2021 (i.e., due to the fact that they are constructed in accordance with the standard DIN EN 13445-3:2021).

[0054] In the case where a component resistant to impact pressure is connected via a valve (especially a rotary valve / feeder) to a component not resistant to impact pressure, these valves are also designed to be resistant to impact pressure and thus explosion-proof. In some embodiments, the valves are also designed (constructed) completely or partially in accordance with the standard DIN EN 13445-3:2021. Thereby, the entire equipment area including the components affected by a possible explosion can be designed to be resistant to impact pressure and still be connected to the remaining equipment components by means of these impact pressure-resistant valves. Such an entire equipment area can be designed for an impact pressure exceeding atmospheric pressure by up to 10 bar in the case of a dust explosion hazard.

[0055] In some embodiments, at least the second comminution device and its inlets and outlets (including the corresponding valves arranged at these inlets and outlets) are designed to be resistant to impact pressure and thus explosion-proof.

[0056] In some embodiments, when a rotor impact mill is used as the second comminution device, the circumferential speed or tip speed of the rotor impact mill is controlled and adjusted in a suitable manner to achieve explosion protection. In some embodiments, the circumferential speed or tip speed of the rotor impact mill is controlled and adjusted within a range of 20 - 120 meters per second (20 m / s - 120 m / s). In some embodiments, the circumferential speed or tip speed of the rotor impact mill is controlled and adjusted within a range of 30 - 80 m / s. In some embodiments, the circumferential speed or tip speed of the rotor impact mill is controlled and adjusted within a range of 40 - 60 m / s. However, it should be noted that the power impact depends on the construction size and circumferential speed of the rotor impact mill as well as the material fed in, and thus can be adjusted accordingly.

[0057] To achieve explosion protection, in still other embodiments, shut-off valves, in particular quick-closing valves, are provided in some or each exhaust duct / exhaust pipeline of the equipment. Alternatively or additionally, the length of some or all of the exhaust pipelines is selected in such a way that the pressure can be released along the length of the corresponding exhaust pipeline. It should be noted that at least some of the first comminution device, drying device, second comminution device, and pyrolysis device include at least one exhaust pipeline. Pressure measuring devices can be provided to detect the prevailing pressure in the equipment, in particular in the corresponding components of the equipment affected by a possible explosion and / or in the corresponding exhaust ducts, and to control the corresponding quick-closing valves / flaps.

[0058] In still other embodiments, the transfer device for transferring the comminuted battery material from the first comminution device to the intermediate storage device and / or the transfer device for transferring the comminuted battery material from the intermediate storage device to the drying device and / or the transfer device for transferring the dried battery material to the second comminution device and / or the transfer device for transferring the dried and comminuted battery material from the second comminution device to the pyrolysis device are designed to be shock-pressure resistant and are connected to the corresponding adjacent devices in a shock-pressure resistant manner. For example, the corresponding transfer device is structurally designed to withstand a pressure up to 10 bar higher than the ambient pressure, i.e., to be resistant to a pressure up to 10 bar higher than the ambient pressure.

[0059] All these measures, either individually or in combination, provide explosion protection and ensure that in the equipment according to the present disclosure, substantially unprepared batteries, in particular batteries without or at least without complete pre-discharge and disassembly, can be recycled in a substantially automated and thus cost-effective process.

[0060] In an exemplary device, 4 tons of waste batteries can be recycled per hour. The waste batteries are supplied to the first shredding device, for example, in the form of forty batches of 100 kg, and are temporarily stored in an intermediate storage device, for example, before they are conveyed to the drying device. The shredded battery material can be compacted by a conveying device (such as a tubular screw conveyor), which transports the material to the drying device. As a conventional drying device (such as a negative pressure drying device that dries the battery material at a pressure below ambient pressure, for example, 50 hPa, and a temperature of at least 120 °C), it can only process 2 tons of battery material per hour. Two such drying devices are arranged downstream of the first shredding device, which is formed by a combination of two shredders connected in series (for example, a primary shredder (pre-shredder) and a subsequent secondary shredder (such as a universal shredder of type NGU 0513 sold by BHS Sonthofen GmbH of Germany)). Since the rotor impact mill forming the second shredding device can usually also only process 2 tons of battery material per hour, two such rotor impact mills are provided downstream of the first shredding device formed by two shredders connected in series.

[0061] In order to prevent environmentally incompatible or even dangerous gases from escaping from the battery recycling device, in other embodiments of the device, it is proposed that the first shredding space and / or the intermediate storage space and / or the drying space and / or the second shredding space and / or the at least one separation device is airtight.

[0062] In other embodiments, the transfer device for transferring the shredded battery material from the first shredding device to the intermediate storage device and / or the transfer device for transferring the shredded battery material from the intermediate storage device to the drying device and / or the transfer device for transferring the dried battery material to the second shredding device and / or the transfer device for transferring the dried and shredded battery material from the second shredding device to the pyrolysis device is airtight and is connected in an airtight manner to the corresponding device adjacent thereto. Therefore, any transfer device for transferring and / or transferring the processed battery from any separation device located between the first shredding device and the drying device and / or between the drying device and the second shredding device and / or between the second shredding device and the pyrolysis device is airtight and is connected in an airtight manner to the corresponding device adjacent thereto.

[0063] In other embodiments, an exhaust gas treatment device is provided that is connected via a respective exhaust gas pipeline to any one of a first comminution space, and / or an intermediate storage space, and / or a drying space, and / or a second comminution device, and / or to at least one separation device positioned between the drying device and the second comminution device and / or between the second comminution device and the pyrolysis device via a gas supply pipeline, and is configured to treat gases formed in the first comminution space, and / or in the intermediate storage space, and / or in the drying space, and / or in the second comminution space, and / or in any one of the at least one separation device positioned between the drying device and the second comminution device and / or between the second comminution device and the pyrolysis device. Those skilled in the art are familiar with the components that an exhaust gas treatment device may or should include depending on the gas components generated. For this reason, a detailed discussion of the design and function of the exhaust gas treatment device can be omitted at this time.

[0064] The second comminution device is arranged downstream of the drying device to further comminute the dried battery material to a second degree of comminution. The second degree of comminution is greater than the first degree of comminution provided by the first comminution device. A particle size of up to 20 mm x 20 mm or a particle diameter of up to 20 mm is achieved in the first comminution device, while a particle size in the range of 0.5–3 mm is achieved in the second comminution device. It should be noted that the second comminution device essentially only processes the separator foil and the current collector foil that are part of the dried battery material, while all heavy parts of the dried battery material (such as the housing parts) have been separated out by a properly positioned second separation device located between the drying device and the second comminution device. Furthermore, it should be noted that the active battery material detached from the current collector foil disintegrates as a black substance into particles <250 μm. However, the disintegration of the active battery material is not actually comminution but rather depolymerization. However, the particles with a size <250 μm are included in the battery material produced and exiting in the second comminution device. In the second comminution device, the fed dried battery material is subjected to mechanical pulping by comminution and then granulation, thereby obtaining a second black substance portion with a particle size range <0.25 mm, and the foil is present as granulated particles with a size of 1 - 5 mm (for example 0.5 - 3 mm).

[0065] The pyrolysis device is arranged downstream of the second comminution device. The pyrolysis device is configured to receive the black mass obtained from the comminuted battery material as a first black mass portion from the first comminution device, as a second black mass portion from the second comminution device, and / or as a third black mass portion from the dust collector, and subject the black mass to a heat treatment in a pyrolysis space provided within the pyrolysis device. In some embodiments, the pyrolysis device includes a supply line for supplying an inert gas and / or a reducing gas to the pyrolysis space of the pyrolysis device. In some embodiments of the apparatus, the pyrolysis device includes an oven, such as an electric oven.

[0066] In some embodiments of the apparatus, a filling device is arranged downstream of the pyrolysis device. The filling device provides the pyrolyzed battery material for further processing. In some embodiments, the pyrolyzed battery is filled into a transport container in this filling device.

[0067] In some embodiments, the at least one separation device, which is preferably arranged upstream of the pyrolysis device, is arranged upstream and / or downstream of the second comminution device. In this separation device, the individual components of the waste battery can be separated from each other so as to be supplied to more targeted processing. At least one of the at least one separation device is preferably a sieve. The sieve can be a vibrating sieve. The corresponding separation device can include one or more sieves. Preferably, the corresponding separation device includes more than one sieve.

[0068] In some embodiments, at least one first screening device, which is preferably arranged upstream of the drying device as a first separation device, is arranged downstream of the first comminution device. In this first screening device, only battery material particles having a size of, for example, at most 20 mm x 20 mm (i.e., battery material particles having a particle size of at most 20 mm) are allowed to pass through, while larger particles are retained, i.e., the first separation device has a sieve size of at most 20 mm. Thus, extremely large battery material particles can be prevented from entering the drying device. The first separation device can be designed as a sieve unit (e.g., a perforated sieve), which is arranged as the first separation device at the outlet of the first comminution device. In one embodiment, the openings of the sieve unit have a diameter of about 20 mm. For example, a primary shredder (pre-shredder) in combination with a subsequent secondary shredder (e.g., a universal shredder of type NGU 0513 sold by BHS-Sonthofen GmbH, Germany) can be used as the first comminution device.

[0069] In some embodiments, at least one second separation device, preferably arranged upstream of the second comminution device, is arranged downstream of the drying device. In this second separation device, the battery material obtained from the drying device can be separated into a plurality of parts with different particle sizes, and these parts can be supplied to more targeted downstream processing. Heavy battery material particles (such as steel and / or Al) can be removed and excluded from any further comminution.

[0070] A first part of the active battery material separable due to the at least one second separation device can be directly transferred as a first black mass part to the pyrolysis device. In one embodiment, the first black mass part comprises 1–50% w / w of C. In one embodiment, this first black mass part comprises 20–45% w / w of C. In one embodiment, the first black mass part comprises 30-40% w / w of C. In one embodiment, the first black mass part comprises 0.1–10% w / w of Al. In one embodiment, the first black mass part comprises 1–7% w / w of Al. In one embodiment, the first black mass part comprises 2-4% w / w of Al. In one embodiment, the first black mass part comprises 0.5–7% w / w of Cu. In one embodiment, the first black mass part comprises 1–5% w / w of Cu. In one embodiment, the first black mass part comprises 1.5-3% w / w of Cu. In one embodiment, the first black mass part comprises 0–45% w / w of Mn. In one embodiment, the first black mass part comprises 1.5-30% w / w of Mn. In one embodiment, the first black mass part comprises 3-10% w / w of Mn. In one embodiment, this first black mass part comprises 0.01–65% w / w of Co. In one embodiment, the first black mass part comprises 2-12% w / w of Co. In one embodiment, the first black mass part comprises 3–5% w / w of Co. In one embodiment, the first black mass part comprises 0.01–60% w / w of Ni. In one embodiment, the first black mass part comprises 5–40% w / w of Ni. In one embodiment, the first black mass part comprises 10-20% w / w of Ni. In one embodiment, the first black mass part comprises 1–7% w / w of Li. In one embodiment, the first black mass part comprises 1.5–5.5% w / w of Li. In one embodiment, the first black mass part comprises 2-4% w / w of Li. In one embodiment, the first black mass part comprises 1–7% w / w of F ges 。In one embodiment, the first black mass part comprises 1.5–5.5% w / w of F ges 。In one embodiment, the first black mass part comprises 2-4% w / w of F ges。In one embodiment, the first black material portion comprises 0.1–1.4% w / w of P. In one embodiment, the first black material portion comprises 0.2–1% w / w of P. In one embodiment, the first black material portion comprises 0.4–0.6% w / w of P. In one embodiment, the first black material portion comprises 0–10% w / w of Fe. In one embodiment, the first black material portion comprises 0.05–1% w / w of Fe. In one embodiment, the first black material portion comprises 0.1-0.2% w / w of Fe. The range specifications for the various elements also apply separately to the second black material portion and the third black material portion. The sum of the fractions of the different elements in a black material portion is less than or equal to 100%.

[0071] In certain applications, a combination of waste battery anode materials and waste battery cathode materials is used. In other applications, only waste battery cathode materials are used. The composition of the black material is accordingly changed.

[0072] In some embodiments, at least one third separation device preferably arranged upstream of the pyrolysis device is arranged downstream of the second comminution device. The at least one third separation device is configured to separate battery material particles of different diameters / sizes from the dried and comminuted battery material from the second comminution device into a plurality of different portions of battery material particles according to their respective sizes, i.e., to separate them from each other according to their respective sizes. Each portion is assigned a specific size range different from another portion. The screen / sieve stage (screen / sieve size) is given, for example, as 10 mm, 3 mm, 0.5 mm, 0.25 mm. Additional sieves may also be provided to further classify the battery material particles. Other metal particles (such as Al, Cu, and Fe) in the battery material particles can be removed and excluded from the processing of the pyrolysis device.

[0073] At least one portion of the plurality of different portions, preferably the portion with the smallest particle size <0.25 mm, is transferred as the second black material portion to the pyrolysis device.

[0074] Additional portions can be separated off for transfer to a dust collector, where additional battery material particles accumulate as a third black material portion for transfer to the pyrolysis device.

[0075] The present disclosure also provides a method for recycling waste batteries. The method uses the equipment as described herein and includes

[0076] a) providing waste batteries to a first comminution device,

[0077] b) comminuting the waste batteries in the first comminution device to a first degree of comminution to obtain comminuted battery material,

[0078] c) Transfer the comminuted battery material to a drying device,

[0079] d) Dry the comminuted battery material,

[0080] e) Transfer the dried battery material to a second comminution device,

[0081] f) Under explosion protection conditions, comminute the dried battery material in the second comminution device to a second comminution degree, the second comminution degree being greater than the first comminution degree,

[0082] g) Transfer the dried and comminuted battery material to a pyrolysis device,

[0083] h) Process the dried and comminuted battery material in the pyrolysis device, for example by heating the dried and comminuted battery material to a temperature of 400 °C to 630 °C, for example while bringing the battery material into contact with an inert gas and a reductant gas generated in-situ, to obtain a pyrolyzed battery material.

[0084] At the start of the method, the waste battery is provided to the first comminution device and the second comminution device and then further processed in the pyrolysis device. The first comminution device can be implemented as a combination of a primary shredder and a downstream secondary shredder. For example, a rotor impact mill can be used as the second comminution device.

[0085] At least some, preferably all, of the steps to be carried out between the first comminution device and the pyrolysis device are performed in an inert gas atmosphere. Thereby, explosion protection can be achieved.

[0086] Alternatively or additionally, preferably, all steps to be carried out between the first comminution device and the pyrolysis device are performed in an environment resistant to shock pressure. This means that the corresponding components of the device configured to carry out the corresponding steps are designed to be resistant to shock pressure. Thereby, some embodiments provide a greater wall thickness of the corresponding components and / or thicker bolts and nuts to prevent the walls of the corresponding components from bursting, such that they can withstand greater pressures, for example pressures exceeding atmospheric pressure by up to 10 bar in the presence of a dust explosion hazard. This shock pressure resistant design is also provided for the corresponding connections between components and the transport devices respectively provided on these connections.

[0087] In some embodiments of the method, the waste battery is at least one selected from the group consisting of lithium-ion batteries, lithium-ion battery waste, lithium-ion battery production waste, lithium-ion cell production waste, lithium-ion battery cathode (active) material, lithium-ion battery anode (active) material, and combinations thereof.

[0088] The lithium-ion battery can be disassembled, punched, shredded in a first shredding device (e.g., in at least one industrial shredder), and / or milled in a second shredding device (e.g., in a ball mill, such as in a hammer mill, rotor impact mill, and / or jet mill). Through such mechanical processing, the active battery material of the battery electrodes can be obtained. Different parts of the battery material can be separated from the corresponding residual active battery material, which can also be referred to as "black mass (BM)". The at least one separation device arranged between the first shredding device and the pyrolysis device and based on, for example, forced gas flow, air separation, classification, or screening can be used to remove the light parts (such as the housing parts made of organic plastics and aluminum foil or copper foil). As mentioned above, there can be multiple separation devices, for example, at least one first separation device between the first shredding device and the drying device, and / or at least one second separation device between the drying device and the second shredding device, and / or at least one third separation device between the second shredding device and the pyrolysis device.

[0089] Within the scope of the present disclosure, the term "waste battery" includes battery waste that can originate from, for example, used batteries or production waste (such as defective materials). In some embodiments, the black mass is obtained from the mechanically treated battery waste, for example, from the battery waste treated in a hammer mill, rotor mill, or industrial shredder. Such black mass can have an average particle size (D 50 ) ranging from 1 μm to 1 cm (such as from 1 μm to 500 μm, and further, for example, from 3 μm to 250 μm).

[0090] A larger part of the waste battery (such as the housing, wiring, and electrode carrier film) can be mechanically separated so that the corresponding materials can be excluded from the waste battery used in the method of the present disclosure. In some embodiments, the separation is accomplished by manual or automatic sorting. For example, the magnetic parts can be separated by magnetic separation, and the non-magnetic metals can be separated by eddy current separators. Other techniques can include pneumatic jigs and air tables.

[0091] The battery shredded to the first shredding degree is transferred to a drying device and dried. In some embodiments of the method, the dried battery material includes aluminum foil and active battery material.

[0092] In some embodiments, the dried battery material includes nickel, cobalt, manganese, copper, aluminum, iron, phosphorus, or a combination thereof and active battery material.

[0093] The dried battery material is further shredded in the second shredding device.

[0094] By using at least one separation device arranged between the first comminution device and the pyrolysis device, the comminuted battery material can be separated into different parts, where at least a part of these parts is removed and excluded from the further process. For simplicity, although having different compositions in each method step, the battery material throughout the corresponding further processes is always referred to as battery material. The battery material finally fed into the pyrolysis device is also referred to herein as black mass or black mass portion.

[0095] Subsequently, the comminuted and dried battery material transferred into the pyrolysis device is heated to a temperature of, for example, 400 °C to 630 °C, for example while bringing the comminuted and dried battery into contact with an inert gas and a reducing gas in-situ generated by the thermal decomposition of the comminuted and dried battery material, to obtain the pyrolyzed battery material.

[0096] In some embodiments, the flow rate of the inert gas is in the range of 50 to 250 Sm 3 / h (such as 75 to 200 Sm 3 / h, for example 100 to 150 Sm 3 / h, for example 120 Sm 3 / h (standard cubic meters per hour)).

[0097] In some embodiments, the inert gas contains at least one gas selected from argon (Ar), dinitrogen (N2), helium (He), and mixtures thereof.

[0098] In some embodiments of the method, at least one screw conveyor is used to feed the comminuted and dried battery material into the pyrolysis device, which can be a rotary kiln.

[0099] As provided herein, different process parameters can produce black mass portions as intermediate materials having different compositions and / or properties. Intermediate materials having, for example, favorable compositions, mechanical properties, surface hydrophilicity, and / or porosity can, for example, result in improved processability and / or recovery rates in subsequent downstream processing steps.

[0100] This disclosure also provides a use of the pyrolyzed battery material of this disclosure in the recovery of valuable materials from waste batteries. In some embodiments, the pyrolyzed battery material is used as an intermediate for a downstream leaching process.

[0101] For example, the pyrolyzed black mass portion containing the pyrolyzed battery material can be leached with an acidic aqueous solution containing, for example, sulfuric acid (H2SO4) to obtain a solution containing one or more valuable metal ions. The solution containing one or more valuable metal ions can be further purified via, for example, solvent exchange, ion exchange, precipitation, extraction, and / or electrolysis.

[0102] Without wishing to be bound by theory, it is believed that the pyrolyzed battery material has beneficial properties that improve one or more downstream processes, such as leaching. For example, it is believed that embrittlement of the composite material can result in, for example, smaller particles that have a more beneficial surface-to-volume ratio, which is advantageous for dissolution during acid leaching. The smaller particle size can additionally be beneficial for subsequent transport steps, such as conveying.

[0103] Examples

[0104] The present disclosure will be explained in more detail below based on embodiments with reference to the accompanying drawings.

[0105] Figure 1 FIG. is a schematic view of an embodiment of an apparatus for recycling waste batteries according to the present disclosure. The apparatus for recycling waste batteries is denoted by reference numeral 100. The apparatus 100 includes a first pulverizing device 110, an intermediate storage device 115, a drying device 120, a second pulverizing device 130, a first separation device 112, a second separation device 125, a third separation device 135, and a pyrolysis device 140.

[0106] The apparatus 100 is designed for batch operation. In other words, a predetermined amount of waste batteries (e.g., 100 kg of waste lithium batteries) is supplied to the first pulverizing device 110 through an upstream batching device 101, which is used to divide the incoming waste batteries into individual parts of a predetermined amount.

[0107] The first pulverizing device 110 can be equipped with a sieve device 112 as a first separation device on the outlet side, for example, a perforated plate having holes with a diameter of about 20 mm. To prevent environmentally incompatible gases from escaping from the first pulverizing device 110, the device is preferably airtight. Additionally, the first pulverizing device 110 can be equipped with an inert gas supply line 114 through which inert gas can be supplied from an inert gas supply unit 170 to a first pulverizing space 110a of the first pulverizing device 110, which reduces (if not completely eliminates) the risk of ignition and / or spontaneous combustion of the pulverized battery material.

[0108] After a predetermined residence time in the first comminution device 110, the batteries comminuted to the first comminution degree are conveyed to the intermediate storage device 115. This intermediate storage device 115 is also preferably airtight. Additionally, an inert gas can also be supplied via the feed line 116 from the inert gas supply unit 170 to the intermediate storage device 115 in order to be able to reduce (if not completely eliminate) the risk of ignition and / or self-ignition of the comminuted battery material. The intermediate storage device 115 also has a stirring device that continuously mixes the received and comminuted battery material in the intermediate storage space 115a in order to prevent the formation of overheated partial volumes. In the case where the temperature in the intermediate storage space 115a rises too much, the intermediate storage device 115 also has a cooling device, such as cooling coils through which a cooling medium flows, which are attached to and in thermal exchange contact with the outer boundary wall of the intermediate storage space 115a.

[0109] After the battery material from a predetermined number of comminution processes has been received in the intermediate storage device 115, the intermediate storage space 115a is emptied in the direction of the drying device 120, the drying space 120a of which is preferably also airtight and can also include a stirring device. Additionally, an inert gas can also be supplied via the line 124 to the drying space 120a.

[0110] In the illustrated embodiment, the drying device 120 is a negative pressure drying device that dries the comminuted battery material at a pressure below the ambient pressure by 50 hPa and at a temperature of at least 120 °C. There are a pressure control unit and a temperature control unit required for this purpose, which are not Figure 1 explicitly designated by reference numerals in the drawings.

[0111] After the comminuted battery material has been dried in the drying device 120, the drying space 120a is emptied in the direction of the second comminution device 130.

[0112] At least one separation device can be arranged downstream of the drying device 120, i.e., upstream and / or downstream of the second comminution device 130, in which the individual components of the comminuted and dried battery material can be separated from each other and thus supplied to more targeted processing. In principle, a plurality of screening stages can be arranged one after another upstream and / or downstream of the second comminution device 130. In some embodiments, one of the screening stages includes a simple sieve.

[0113] In some embodiments, the second separation device 125 may be located between the drying device 120 and the second comminution device 130 to pre - sort the dried battery material before feeding it to the second comminution device 130 and may remove (i.e., sort out and rinse / discharge) heavy parts such as steel and Al particles. A part of the active battery material (the first black - matter part) may be directly transferred to the pyrolysis device 140 via the transfer device 187 as shown by the dashed line without being further comminuted by the second comminution device 130.

[0114] In some embodiments, the second comminution device 130 is equipped with a third separation device 135 on its outlet side, and / or the third separation device 135 may be located downstream of the second comminution device 130 in the direction of the pyrolysis device 140 such that other particles such as Fe, Cu, and Al particles and plastic particles (e.g., PP, PE) can be sorted out and rinsed / discharged. The plastic particles may include diaphragm sheets of different sizes and fragments from the housing part, which may be made of different plastics and partly also have organic filler materials. The remaining undersized battery material is transferred to the pyrolysis device 140 as the second black - matter part.

[0115] To prevent environmentally incompatible gases from escaping from the second comminution device 130, the device 130 is preferably also airtight.

[0116] In addition, the second comminution device 130 is designed to be explosion - proof. Thus, the second comminution device 130 may also be equipped with an inert - gas supply line 134 through which inert gas can be supplied to the second comminution space 130a of the second comminution device 130, which reduces (if not completely eliminates) the risk of ignition and / or self - ignition of the comminuted battery material. The separation devices 125, 135 may also be airtight and / or equipped with corresponding inert - gas supply lines 126, 136.

[0117] Alternatively or additionally, the second comminution device 130 is designed to withstand shock pressure. Thereby, the second comminution device 130 is provided with a larger wall thickness and / or thicker bolts and nuts to prevent the walls of the second comminution device 130 from rupturing such that they can withstand a large pressure, for example, a pressure exceeding the atmospheric pressure by up to 10 bar in the case of a risk of dust explosion.

[0118] The battery material comminuted to a second degree in the second comminution space 130a of the second comminution device 130 and preferably sorted and released from the sorted - out parts is transferred to the pyrolysis device 140 as the second black - matter part. The first black - matter part from the second separation device 125 and the second black - matter part from the third separation device 135 may be combined before being fed to the pyrolysis device 140 or fed to the pyrolysis device 140 as separate parts.

[0119] The pyrolysis device 140 receives in a pyrolysis space 140a the comminuted, dried and optionally sieved battery material as a black mass, where the black mass is subjected to a heat treatment under reducing conditions to obtain a pyrolyzed battery material.

[0120] A further sieving device 150 may be arranged downstream of the pyrolysis device 140, in which different parts of the pyrolyzed battery material can be separated from one another and thus supplied to a more targeted processing. In principle, a plurality of sieving stages can be arranged one after the other. In some embodiments, one of the sieving stages comprises a simple sieve.

[0121] Finally, the pyrolyzed battery material can be filled in a filling device 160 into transport containers 161, 162.

[0122] It should also be noted that in some embodiments, not only the first comminution device 110, the intermediate storage device 115, the drying device 120, the second comminution device 130, and the pyrolysis device 140 can be made airtight, but also the separation devices 112, 125, 135 and the transfer devices 181, 182, 183, 184, 185, 186 and 187 (these transfer devices transfer the comminuted battery material between the corresponding devices of the equipment, for example from the first comminution device 110 to the intermediate storage device 115 (transfer device 181), from the intermediate storage device 115 to the drying device 120 (transfer device 182), from the drying device 120 to the second separation device 125 (transfer device 183), from the second separation device 125 to the second comminution device 130 (transfer device 184), from the second comminution device 130 to the third separation device 135 (transfer device 185), from the third separation device 135 to the pyrolysis device 140 (transfer device 186), and / or from the second separation device 125 directly to the pyrolysis device 140 (transfer device 187)) can also be made airtight respectively.

[0123] It should also be noted that potentially environmentally harmful gases formed in the first comminution device 110, the intermediate storage device 115, the drying device 120, the second comminution device 130, and the pyrolysis device 140 can be supplied via pipelines 191, 192, 193, 194, 195 to an exhaust gas treatment device 190 of a known type, in which these gases are treated in an environmentally friendly manner.

[0124] In addition, it should be noted that at least one of the first comminution device 110, the intermediate storage device 115, the drying device 120, and the second comminution device 130 is made resistant to impact pressure, and the separation devices 112, 125, 135 and the transfer devices 181, 182, 183, 184, 185, 186 and 187 (which transfer the comminuted battery material between the corresponding devices of the equipment, for example from the first comminution device 110 to the intermediate storage device 115 (transfer device 181), from the intermediate storage device 115 to the drying device 120 (transfer device 182), from the drying device 120 to the second separation device 125 (transfer device 183), from the second separation device 125 to the second comminution device 130 (transfer device 184), from the second comminution device 130 to the third separation device 135 (transfer device 185), from the third separation device 135 to the pyrolysis device 140 (transfer device 186), and / or from the second separation device 125 directly to the pyrolysis device 140 (transfer device 187)) can also be made resistant to impact pressure respectively.

[0125] The third separation device 135 is connected to the dust collector 197 via a gas pipeline 196. The pyrolysis space 140a is also connected to the dust collector 197 via a gas pipeline 198.

[0126] Finally, it should be noted that all of the above-mentioned devices of the battery recycling equipment 100 can have associated inlet and / or outlet double gate locks ( Figure 1 not shown in the figure).

[0127] Figure 2An exemplary second comminution device 130, which is part of an exemplary recycling device according to the present disclosure, is shown schematically. Accordingly, a transfer device 184 equipped with a rotary feeder 201 is provided for feeding dried battery material from a drying device 120 (not shown here) into a second comminution space 130a of the second comminution device 130, where the second comminution device 130 is a rotor impact mill. The outlet of the rotor impact mill 130 is in fluid flow connection with a third separation device 135 via a transport device 185. The third separation device 135 is in fluid flow connection with a pyrolysis device 140 via a transport device 186. The battery material particles accumulated in the third separation device 135 are fed as a second black material portion into the pyrolysis device 140 (not shown here) via a transport device 186 using a rotary feeder 202. In the embodiment shown here, the third separation device 135 is coupled to a dust collector 197 via a gas line 196. The third separation device 135 is exemplarily designed as a sieve and is arranged downstream of the second comminution device 130 and is configured to separate battery material particles within a desired size range for transfer to the dust collector 197. These battery material particles are transferred to the dust collector 197 via a transport line 196 using a blower so that no dust can escape into the ambient air. These battery material particles are collected in the dust filter 197 and can also be fed as a third black material portion into the pyrolysis device 140 via a transport line 198 (not shown here).

[0128] List of reference numerals

[0129] 100 Device

[0130] 101 Batching device

[0131] 110 First comminution device

[0132] 110a First comminution space

[0133] 112 First separation device

[0134] 114 Inert gas supply line

[0135] 115 Intermediate storage device

[0136] 115a Intermediate storage space

[0137] 116 Inert gas supply line

[0138] 120 Drying device

[0139] 120a Drying space

[0140] 124 Inert gas supply line

[0141] 125 Second separation device

[0142] 126 Inert gas supply pipeline

[0143] 130 Second comminution device

[0144] 130a Second comminution space

[0145] 134 Inert gas supply pipeline

[0146] 135 Third separation device

[0147] 140 Pyrolysis device

[0148] 140a Pyrolysis space

[0149] 150 Screening device

[0150] 160 Filling device

[0151] 161 Transport container

[0152] 162 Transport container

[0153] 170 Inert gas supply unit

[0154] 181 Transfer device

[0155] 182 Transfer device

[0156] 183 Transfer device

[0157] 184 Transfer device

[0158] 185 Transfer device

[0159] 186 Transfer device

[0160] 187 Transfer device

[0161] 190 Exhaust gas treatment device

[0162] 191 Pipeline to exhaust gas treatment device

[0163] 192 Pipeline to exhaust gas treatment device

[0164] 193 Pipeline to exhaust gas treatment device

[0165] 194 Pipeline to exhaust gas treatment device

[0166] 195 Pipeline to exhaust gas treatment device

[0167] 196 Transport pipeline

[0168] 197 Dust collector

[0169] 198 Transportation pipeline

[0170] 201 Rotary feeder

[0171] 202 Rotary feeder

Claims

1. An apparatus (100) for recycling waste batteries, comprising: - A first comminution device (110) for comminuting waste batteries to a first comminution degree in a first comminution space (110a) to obtain comminuted battery material; - A drying device (120) arranged downstream of the first comminution device (110) for drying the comminuted battery material; - A second comminution device (130) arranged downstream of the drying device (120) for comminuting the dried battery material to a second comminution degree in a second comminution space (130a), the second comminution degree being greater than the first comminution degree; And - A pyrolysis device (140) arranged downstream of the second comminution device (130) for pyrolyzing the dried and comminuted battery material in a pyrolysis space (140a), wherein at least the second comminution device (130) is designed to be explosion-proof.

2. The device according to claim 1, wherein In order to be explosion-proof, at least the second comminution device (130) is mechanically designed to withstand a pressure up to 10 bar above ambient pressure.

3. The device according to claim 2, wherein In order to be explosion-proof, at least the second comminution device (130) is constructed completely or partially in accordance with the standard DIN EN 13445-3:2021.

4. The device according to any one of the preceding claims, wherein, The second comminution device (130) is an impact mill.

5. The device according to claim 4, wherein The second comminution device (130) is a rotor impact mill, wherein, in order to be explosion-proof, the circumferential speed or tip speed of the rotor impact mill is controlled and adjusted within a range of 20 - 120 meters per second (20 m / s – 120 m / s), particularly within a range of 30 – 80 m / s, more particularly within a range of 40 – 60 m / s.

6. The device according to claim 4 or 5, wherein In order to be explosion-proof, the minimum thickness of the rear wall of the grinding chamber of the impact mill is given as follows: where d min is the minimum thickness of the rear wall, C1 is a proportionality coefficient, D is the equivalent diameter of the rear wall, p is the maximum expected pressure in the grinding chamber, and f is the existing / allowable tensile stress in the construction material of the rotor impact mill.

7. The apparatus according to any one of the preceding claims, wherein, At least the second comminution device (130) is equipped with at least one supply line (134) for supplying an inert gas to the second comminution space (130a) of the second comminution device (130).

8. The apparatus according to any one of the preceding claims, wherein, At least the second comminution space (130a) is airtight.

9. The apparatus according to any one of the preceding claims, wherein, One or more of the transfer devices for transferring the dried and comminuted battery material from the second comminuting device (130) to the pyrolysis device (140) or for transferring the dried battery material from the drying device (120) to the second comminuting device (130) are airtight and are connected in an airtight manner to the adjacent devices, wherein each of the inlet and outlet of the second comminuting device (130) and / or each of these transfer devices adjacent to the second comminuting device (130) is mechanically designed to withstand a pressure up to 10 bar higher than the ambient pressure. The transfer device is preferably any rotary feeder configured to feed the dried battery material to the second comminuting device (130) and / or transfer the comminuted battery material from the second comminuting device (130) in the direction of the pyrolysis device (140), and / or any valve configured to supply any conveying gas to the second comminuting device (130) and / or discharge exhaust gas from the second comminuting device (130).

10. The apparatus according to any one of the preceding claims, further comprising an exhaust gas treatment device (190), which is connected via corresponding gas supply pipelines (191, 193, 194) to one or more of the first comminuting space (110a), the drying space (120a) of the drying device (120), or the second comminuting space (130a) of the second comminuting device (130), and is configured to treat the gas formed in one or more of the first comminuting space (110a), the second comminuting space (130a), or the drying space (120a).

11. The apparatus according to any one of the preceding claims, further comprising at least one shut-off valve, in particular a quick-acting valve, in some or each exhaust gas pipeline of the apparatus, which is controlled by a pressure measuring device.

12. The apparatus according to any one of the preceding claims, further comprising at least one separating device (112, 125, 135) upstream of the pyrolysis device (140), the at least one separating device comprising a sieve unit as a first separating device (112) arranged at the outlet of the first comminuting device (110), at least one screening device as a second separating device (125) arranged upstream of the second comminuting device (130) and downstream of the drying device (120), and / or at least one screening device as a third separating device (135) arranged downstream of the second comminuting device (130).

13. The device according to any one of the preceding claims, further comprising a dust collector (197) coupled to at least the second comminution device (130) and / or to at least one separation device (112, 125, 135), the dust collector including a blower, a dust filter, and a dust receiver, and being configured to remove / extract dust-laden air from the second comminution device (130) and / or the corresponding separation device (112, 125, 135).

14. The device according to any one of the preceding claims, further comprising a filling device (160) arranged downstream of the pyrolysis device (140).

15. A method for recycling waste batteries, the method using the device according to any one of the preceding claims, and at least comprising: a) providing waste batteries to the first comminution device (110), b) comminuting the waste batteries in the first comminution device (110) to a first comminution degree to obtain comminuted battery material, c) transferring the comminuted battery material to the drying device (120), d) drying the comminuted battery material, e) transferring the dried battery material to the second comminution device (130), f) comminuting the dried battery material in the second comminution device (130) to a second comminution degree, the second comminution degree being greater than the first comminution degree, g) transferring the comminuted and dried battery material to the pyrolysis device (140), h) processing the comminuted and dried battery material in the pyrolysis device (140).

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