Method and device for recovering black mass from a mixture of fragments of components of battery cells

Abstract

A method and a device for recovering black mass from a mixture of fragments of components of battery cells, as well as a system for recovering black mass from a suitable starting material, in which the device according to the invention is used, are provided.

Description

[0001] FRAUNHOFER-GESELLSCHAFT...eV, Viridis Innovation GmbH P150453PC00

[0002] Method and apparatus for obtaining black mass from a mixture of fragments of battery cell components

[0003] A method and a device for obtaining black mass from a mixture of fragments of battery cell components, as well as a system for obtaining black mass from a suitable starting material, in which the device according to the invention is used, are provided.

[0004] Processes, devices, and systems of this type are used in the recycling of secondary batteries made from battery cells. The mixture of fragments is obtained in the system from a suitable starting material, whose components are appropriately separated and thereby crushed into fragments.

[0005] Within the scope of the present invention, a suitable starting material is understood to be a mixture containing at least one of the following components: battery cells, pre-products generated or used in the manufacture of battery cells, insofar as black mass can be obtained from the pre-products, offcuts of these pre-products, production waste from the manufacture of batteries, electric vehicles and other electrical equipment, insofar as black mass can be obtained from the production waste.

[0006] The intermediate products are, for example, foils with electrode material, battery cells not filled with electrolyte, defective battery cells and / or reject active material.

[0007] Within the scope of the present invention, the term "battery cells" is understood to include both battery cells obtained by dismantling used batteries that, for example, have reached the end of their service life, and battery cells that were identified as rejects before or after their assembly into batteries (i.e., also as good as new, but declared as rejects).

[0008] These types of battery cells are chemical energy storage devices for the reversible storage of electrical energy. Examples of these battery cells include lithium-ion battery cells, sodium-ion battery cells, zinc-carbon battery cells, nickel-metal hydride battery cells, and nickel-cadmium battery cells.

[0009] These battery cells contain two electrodes, an anode and a cathode, a separator for electrical separation of the electrodes, and an electrolyte for ion transport. The separator either acts as the electrolyte itself or is impregnated with a liquid electrolyte. These components are located inside a housing, which has external contacts for connecting the electrodes and seals the interior airtight.

[0010] The starting material can contain battery cells with and / or without a casing, i.e., only the battery cores.

[0011] Several such battery cells can be enclosed in a common casing and assembled into a battery cell module, in which they can be connected in series and / or parallel.

[0012] Battery cells and / or battery cell modules are located in rechargeable batteries, battery modules and battery systems, which are referred to simply as secondary batteries within the scope of the present invention and can be charged and discharged at least once, usually several times.

[0013] In the context of this application, the term "black mass" refers to a material that essentially contains or consists of the material of the cathode and anode, i.e., the active material of the cathode and the anode. The material referred to as active material is the material capable of storing electrical energy through the uptake of ions.

[0014] The active material consists primarily of lithium, nickel, and cobalt. Graphite, SiOx, and metallic lithium are used as anode active materials, while LiNiMnCoCh, LiNiAICoCh, LiFePO4, and LiMn2O4 are used as cathode active materials. Within the scope of this application, the terms anode material and anode active material, as well as cathode material and cathode active material, are used synonymously.

[0015] The terms electrode material and electrode active material are used as a general term for the anode and cathode material or the anode and cathode active material.

[0016] For the purposes of this application, the term “other components” of the starting material means other components of battery cells or their intermediate products, in particular the separators, current collectors and the casings, or parts thereof, but not a liquid electrolyte.

[0017] The current collectors, also known as current-collecting foils, are coated with the anode or cathode material, which is also formed as foils, and consist of a current collector material that includes, in particular, copper (anode) or aluminum (cathode).

[0018] The use of secondary batteries, such as lithium-ion batteries (LIBs), has been increasing rapidly for years, with applications ranging from small appliances to electric vehicles. However, the development of suitable recycling processes for used batteries is not keeping pace, even though the requirements for recycling quotas and the use of recycled materials will increase significantly in the coming years.

[0019] The demand for efficient processes for recycling lithium-ion batteries with high yields and high-quality recycled products is therefore high.

[0020] It is known from JP 2024020288 A to recycle LIBs pyrometallurgically. In this process, the secondary batteries are treated in blast furnaces at temperatures sometimes exceeding 1000 °C (with optional carbon addition). The metal oxides are reduced and subsequently melt, allowing them to be recovered. However, this process has the disadvantage of being very energy-intensive and generating significant emissions of greenhouse gases and other pollutants, making it neither very economical nor environmentally friendly.

[0021] From CN 108075203 B, another pyrometallurgical process is known in which secondary batteries are first amorphized at very high temperatures (>800 °C) under exclusion of air and then shredded.

[0022] Pure hydrometallurgical processes are also known from AU 2019 459228 B2. For this, the secondary batteries are first shredded and then dissolved in acids. EP 4447 194 Al discloses a process for recycling battery components, in which battery cells are first cut into individual parts, then the electrolyte is washed out of said parts in a perforated drum, and finally the washed parts, freed from the electrolyte, are separated from each other by electrohydraulic comminution.

[0023] This method has the disadvantage that the washing step only removes the electrolyte from the cut parts by rinsing, making a subsequent step of separating other battery cell components (e.g., the electrode active material) complex and time-consuming. Furthermore, this method does not allow for the quick and easy separation of a large portion of the liquid containing the electrode active material from the electrode active material itself.

[0024] Furthermore, the process has the disadvantage that the anode material, cathode material, separator, and current collectors are cut into small pieces. On the one hand, particles from the separator and current collectors can enter the black mass, resulting in a black mass of lower purity from which the contaminating particles are subsequently difficult to separate. On the other hand, the components of the battery cells are mechanically shredded, which makes their reuse in new battery cells more difficult and less economical.

[0025] The prevailing recycling method for lithium-ion batteries (LIBs) in the state of the art is therefore mechanical pretreatment, in particular shredding in a shredder or mill. The battery modules, including housings, plastics, adhesives, and cells, are typically shredded into particles ranging in size from millimeters to micrometers. Separation processes such as magnetic separation, flotation, and filtration are used to recover the cathode, anode, and current collector material.

[0026] However, these processes have significant drawbacks. For example, the high mechanical stresses, forces, and temperatures involved can burn or destroy the materials, rendering some of them unrecyclable. Furthermore, the resulting electrode materials often contain high levels of metallic impurities, such as copper, steel, and / or aluminum. In addition, material losses in these processes range from 20% to 40%, limiting the overall efficiency to below 80%.

[0027] Furthermore, the recovered electrode materials (black mass) contain impurities that necessitate additional post-treatment steps, such as sieving, cleaning, and leaching, increasing the cost and effort of the process. Moreover, these processes carry a risk of releasing hazardous substances, such as electrolytes and heavy metals, requiring careful handling and safety precautions.

[0028] In DE 102015216932 Al a process for recycling composite materials is described in which composite materials such as glass, semiconductors, metal and polymers present in a liquid medium are subjected to electrohydraulic comminution and then separated from each other and from the liquid medium in a physical separation step.

[0029] Examples of composite materials include glass, semiconductors, metals and polymers; examples of physical separation steps include sieving, filtering, washing, dispersing, sedimenting, flotation, density separation, aerocurrent sorting, magnetic separation, eddy current separation, optical separation, sensor-based separation, electrophoretic separation, electrostatic separation and combinations thereof.

[0030] The composite materials should originate from waste or production rejects of thin-film batteries, solid-state batteries, polymer batteries, displays, light-emitting diodes, superconductors, magnetic functional materials, polymer-coated or polymer-bonded magnets, metallized plastics, metallized glasses, polymer-coated glasses or mixtures thereof.

[0031] The electrohydraulic comminution of CdTe solar cells is given as an example, without the individual process parameters being described in a way that allows for further analysis.

[0032] Based on this, the object of the present invention was to provide a method, a device, and a system with which it is possible to overcome at least one disadvantage known in the prior art. In particular, the method and the system should make it possible to obtain black mass in the highest possible purity in a simpler, faster, more cost-effective (i.e., more economical), more environmentally friendly (i.e., more ecological), and / or safer manner for operators.

[0033] The problem is solved by the method with the features of claim 1, the device with the features of claim 15, and the system with the features of claim 22. The dependent claims describe advantageous embodiments.

[0034] According to the invention, a method for obtaining black mass from a mixture of fragments of battery cell components is provided, comprising the steps:

[0035] a) Providing a launching system containing the mixture dispersed in a liquid,

[0036] b) Filtering the starter system through a multi-pore filter device and collecting the filtered starter system as process water containing unfiltered fragments,

[0037] c) Centrifuging the process water to separate the process water from the unfiltered fragments, and

[0038] d) Transferring the fragments separated during centrifugation as black mass into a first container,

[0039] wherein the pores have dimensions adapted to the dimensions of the fragments in the mixture such that at least 90%, preferably at least 95% of the fragments of anode and / or cathode material contained in the starting system can pass through the pores, wherein the pores preferably have a diameter of < 2 mm, further preferably in the range of 0.01 mm to 1 mm, further preferably of approximately 0.5 mm.

[0040] In the context of the present invention, the term "starting system" refers to a liquid containing a mixture of fragments distributed or absorbed therein.

[0041] In this way, black mass with very high purity can be obtained, which depends on the matching of pore and fragment dimensions. The fragments in the selected starting system exhibit significant differences in the dimensions of the electrode active material fragments and the fragments of the other components, thus enabling a simple, purely mechanical separation with high separation efficiency.

[0042] Furthermore, this process yields pure process water that contains only salts (electrolyte) and possibly the electrolyte (hydrocarbon compounds); the expression "can pass" indicates that the filtration process can be integrated into a cycle.

[0043] It is preferred that the filter device has a tubular drum with a horizontal axis of rotation and a shell in which the pores are arranged, and that the drum is rotated about the horizontal axis of rotation, preferably with at least one vane arranged inside the shell, and that when the drum is rotated the liquid and the mixture distributed in it are transported in the direction of the axis of rotation and the fragments are loosened, for which purpose the drum is further preferably rotated in step b) at a speed between 0.1 and 100 rpm.

[0044] The drum can be a cylindrical or a conical tube. The separation of filtered fragments (i.e., those retained) and unfiltered fragments (i.e., those passing through the pores) occurs by gravity, with the impeller providing a washing effect. This effect is further enhanced in a conical drum because the impeller moves the fragments like a screw against the inclined plane inside the drum. The advantage here is that a very high degree of separation is achieved simply, especially when the fragments are not produced by shredding battery cells. The pores in filters are generally round or rounded and can be described by the diameter of the circle, which determines the separation efficiency. If, on the other hand, the pores are oval or rectangular, the diameter, within the scope of the present invention, refers to the clear width of the pores, which determines the separation efficiency.

[0045] In the chosen starting system, there is a large difference between the fragments of the active materials (approx. 2 - 50 µm on average) and the fragments of the remaining components (> 2 mm) of the battery cells, because the fragments are not produced by mechanical comminution (shredding or cutting), but by comminution with shock waves.

[0046] The use of electro-hydraulic shredding is particularly advantageous. This results in high purity because extremely precise sorting by size is possible.

[0047] The rotation of the drum and the wings transport and mix the fragments, preventing the pores from becoming clogged.

[0048] It is particularly preferred if the filtering process in step b) has at least a first and a second time period, wherein the rotational speed of the drum during the first time period is different from the rotational speed of the drum during the second time period.

[0049] The advantage here is that during the initial period of 1 to 20 minutes and at a slow rotational speed of 0.1 to 0.5 rpm, fragments floating on the liquid in the drum can be effectively collected. Simultaneously, a large proportion of the fragments of electrode active material are washed through the pores.

[0050] Therefore, it is preferred if a skimming device is arranged in the drum, which skims off fragments floating on top of the liquid and transports them out of the drum. During the second period of 1 to 15 minutes, the drum rotates at a higher speed between 5 and a maximum of 60 rpm, resulting in greater friction between the remaining fragments, which then separate from each other and can now pass through the pores.

[0051] Furthermore, it is preferred if, during or after step b), a rinsing fluid is sprayed onto the jacket from the inside and / or outside, preferably under a pressure between 1.1 and 250 bar.

[0052] The advantage here is that the pores are cleaned and adhering fragments are loosened. This measure also improves the filter's effectiveness and prevents the pores from clogging. The rinsing fluid can be recycled process water or an additional solution. Because the rinsing fluid is sprayed under pressure, even mechanically adhering fragments are resuspended.

[0053] The larger fragments that remain in the drum after filtering, which could not be skimmed off and are present as solid material after the liquid has drained from the drum, are removed from the drum after step b) has been completed. The solid material is preferably transported by the vanes arranged inside the drum shell to an opening at the end of the drum.

[0054] It is preferred that in step c) the process water is centrifuged, preferably at a speed between 200 and 5,000 rpm, until a predetermined turbidity level is reached, and the centrifuged process water is then fed back into the drum as rinsing liquid, thereby also separating very small fragments from the process water.

[0055] In step c), centrifugation is preferably carried out until the process water is optically clear, which is assumed to be achieved at a nephelometric turbidity value in the range of < 1 NTU. The nephelometric turbidity value is determined according to DIN EN ISO 7027-1:2016-11. In step a), a suitable starting material containing battery cells and / or battery cell components is preferably provided. The starting material is comminuted by shock waves to obtain a mixture of the component fragments. Preferably, in step a), electrohydraulic comminution of the starting material suspended in an electrically conductive liquid is carried out. A pulsed electrical voltage is applied to the liquid via at least two electrodes to generate the shock waves as lightning discharges. The electrical voltage is preferably

[0056] i) in the range of 20 to 240 kV; and / or

[0057] ii) has a pulse frequency in the range of 0.1 to 200 Hz; and / or iii) causes a discharge that has an energy per electrode and per voltage pulse in the range of > 200 J.

[0058] In this way, unlike when shredding, the mixture contains smaller fragments of anode and cathode material as well as larger fragments of other components. This facilitates the filtering in step b).

[0059] The shock waves are preferably generated according to the electrohydraulic principle, which is based on the generation of shock waves in the form of mass waves in an electrically conductive fluid. Due to their different propagation speeds in different materials, these mass waves damage the components of battery cells, which are made of different materials, primarily at the interfaces where the components are joined. These mass waves can be generated by a lightning discharge in the liquid medium, which abruptly displaces a portion of the mass. As a consequence, a mass or shock wave is created, which propagates through the fluid.

[0060] Furthermore, it is preferred if the starting material is obtained by providing battery cells with casings and providing the casings with at least one opening, the opening preferably being produced by at least one cut through the casing. Here, it is advantageous that the electrohydraulic comminution of the starting material is more efficient than with battery cells that still have their usual, externally airtight casings.

[0061] According to the invention, a device for obtaining black mass from a mixture of fragments of battery cell components is provided.

[0062] The device serves to carry out the method according to the invention and comprises:

[0063] a porous filter device for receiving and filtering a starting system containing the mixture dispersed in liquid,

[0064] a collection device for capturing the filtered start-up system as process water containing unfiltered fragments, and

[0065] a separation system to separate process water and unfiltered fragments from each other and to transfer the separated fragments as black mass into a first container,

[0066] wherein the pores have dimensions adapted to the dimensions of the fragments in the mixture such that at least 90%, preferably at least 95%, of the fragments of anode and / or cathode material contained in the starting system can pass through the pores.

[0067] The pores have a diameter of < 2 mm, preferably in the range of 0.01 mm to 1 mm, more preferably of approx. 0.5 mm, wherein the filter device preferably has a tubular drum with a horizontal axis of rotation and a jacket in which the pores are arranged, and the drum is preferably rotatably driven about the horizontal axis of rotation.

[0068] Preferably, at least one vane is arranged on the inside of the jacket, having an angle of attack perpendicular to the axis of rotation of the drum, in the range of +10° to -10°, wherein a skimming device is preferably arranged in the drum to skim off and transport away fragments floating on top of the liquid. The filter device can have spray nozzles to spray a rinsing liquid onto the jacket, wherein the separation system can include a centrifuge connected to the filter device via a pipe system to feed centrifuged process water into the filter device as a rinsing liquid.

[0069] The advantages associated with these features of the device according to the invention have already been discussed above in connection with the method according to the invention.

[0070] According to the invention, a plant for obtaining black mass from a suitable starting material is also provided, comprising a device for comminuting the starting material with shock waves in order to produce a starting system from a mixture of fragments of battery cell components distributed in a liquid, the device according to the invention for sorting separated anode and cathode material as black mass into a first container, and a control unit for controlling the plant.

[0071] The device for comminuting the starting material comprises a trough for receiving the starting material in an electrically conductive liquid and at least two electrodes, wherein the control unit is configured to apply a pulsed electrical voltage to the liquid via the at least two electrodes, which preferably

[0072] i) in the range of 20 to 240 kV; and / or

[0073] ii) has a pulse frequency in the range of 0.1 to 200 Hz; and / or iii) causes a discharge that has an energy per electrode and per voltage pulse in the range of > 200 J.

[0074] The system also includes a device for receiving secondary batteries and a disconnecting device, wherein the control unit is configured to cause the disconnecting device to disconnect battery cell modules and / or battery cells contained in the received secondary batteries from other components of the secondary battery, wherein an opening device is further provided for producing at least one opening in a housing of battery cells, wherein the openings between the interior of the housing and the exterior of the housing establish a fluid-conducting connection, wherein the control unit is configured to cause the opening device to produce at least one such opening in the housing of the battery cells.

[0075] The advantages associated with these features of the system according to the invention have already been discussed above in connection with the method according to the invention.

[0076] The inventive method thus makes it possible to obtain black mass in high purity in a simpler, faster, more cost-effective (i.e. more economical), more environmentally friendly (i.e. more ecological) and safer manner for operators.

[0077] For example, the process does not require thermal treatment at high temperatures, making it simpler, faster, and more cost-effective. Furthermore, the process does not release greenhouse gases, allowing for a more environmentally friendly approach. Additionally, the process does not use hazardous chemicals, making it safer.

[0078] Apart from this, the process does not include a step in which the anode material, the cathode material, and the current collectors (optionally also a separator) of the battery cells are cut into parts. This allows for larger portions of these battery cell components (down to their original size) to be provided. Furthermore, this allows for the provision of black mass in a purer form, as contamination caused, for example, by shredding in the prior art is avoided.

[0079] In the context of this application, separation means that previously joined, different components are separated from one another at their material boundaries or interfaces and, if necessary, broken down into smaller parts. After this separation, the parts are present in a mixture in which the various components of battery cells are largely separated from one another and exist as fragments, which can also be described as particles or parts. Sorting, in the context of this application, means that the previously separated parts are placed in containers, with at least one separate container for each component or at least one common container for the components of several components.

[0080] The electrolyte in battery cells can be a liquid or solid electrolyte. A liquid electrolyte can be separated very quickly and easily from other battery components during the grinding process, as the liquid electrolyte dissolves in or mixes with the liquid.

[0081] Furthermore, the battery cells can contain an electrolyte-impregnated separator, which preferably contains or consists of a plastic and is optionally provided with a ceramic coating. A separator containing or consisting of plastic offers an advantage in the new process because it can be more easily separated from the other battery cell components using a separation method based on the different specific densities of the battery cell components. For example, if an electrically conductive liquid with a density of approximately 1 g / cm³ is used... 3When used for sorting, the separators and their fragments float on the surface of the liquid and can be suctioned, skimmed off, and / or scooped out. This process is also known as skimming.

[0082] The following examples and figures are intended to explain the subject matter of the invention in more detail, without limiting it to the specific embodiments shown here.

[0083] Exemplary embodiments of the invention are shown in the figures and explained in more detail in the description below.

[0084] They show

[0085] Fig. 1 shows a schematic representation of a secondary battery;

[0086] Fig. 2 shows a schematic representation of a battery cell installed in the secondary battery;

[0087] Fig. 3 shows a schematic representation of the new plant for the production of black mass, on which the new process is carried out;

[0088] Fig. 4 shows a schematic side view of an opening device for battery cell housings used in the system shown in Fig. 3;

[0089] Fig. 4a shows a battery holder with a battery cell inserted therein, the head and bottom of which are removed with the opening device from Fig. 4;

[0090] Fig. 5 shows a schematic side view of a device used in the system from Fig. 3 for carrying out electrohydraulic comminution;

[0091] Fig. 6 intact battery cells and their components after electrohydraulic comminution;

[0092] Fig. 7 shows a schematic side view of a sorting system used in the system from Fig. 3, with a drum serving as a filter;

[0093] Fig. 8 shows a top view of the inside of the drum shell from Fig. 7;

[0094] Fig. 9 shows a view of the drum from Fig. 7 from the right; and

[0095] Fig. 10 is a schematic side view of the drum from Fig. 7 in longitudinal section.

[0096] Fig. 1 shows a schematic representation of a multi-rechargeable battery system, which is also referred to as a secondary battery 10 within the scope of the present application. The secondary battery 10 consists, in a manner known per se, of a battery housing 11 in and on which various components are arranged, including, internally, an electronic control unit 12 and several battery cell modules 14, each with its own casing 15, and externally, electrical connections 16.

[0097] The battery housing 11 also contains cooling systems, mounting frames, wiring and other components which are known in themselves and are not shown for the sake of clarity.

[0098] Within the casing 15 of each battery cell module, several battery cells 17 are arranged, electrically connected in series and / or parallel. In the illustrated embodiment, these cells are cylindrical. Besides cylindrical battery cells, prismatic battery cells and so-called pouch battery cells are also known and are likewise used in rechargeable batteries.

[0099] Fig. 2 shows, at the top, a schematic, partially cutaway three-dimensional view of the battery cell 17 from Fig. 1 with its cylindrical housing 18, including a battery jacket 18a and a wound, three-layer battery core 19 located inside 20 of the housing 18. In Fig. 2 below, the battery core 19 is unwound and shown in detail.

[0100] The battery core 19 contains a double layer of anode material 22 serving as an anode 21, a double layer of cathode material 24 serving as a cathode 23 and in between a layer of separator material 26 serving as a separator 25.

[0101] The separator 25 serves to electrically separate the electrodes, i.e., anode 21 and cathode 22, and contains an electrolyte indicated at 27 for ion transport.

[0102] Anode material 22 and cathode material 24 are laminated as foil on both sides onto current collectors 28, which act as current collecting foils and consist of a current collector material 29, which in the case of the anode 21 consists entirely or substantially of copper and in the case of the cathode consists entirely or substantially of aluminium.

[0103] It is also known to laminate anode and cathode material 22, 24 only on one side of the current collectors 28.

[0104] The separator 25 can either act as the electrolyte itself or be impregnated with a liquid electrolyte 27. A first terminal 30 of the battery cell 17, made of a suitable material, is located on the outside of the housing 18. The outer surface of the housing 18 acts as the second terminal of the battery cell 17.

[0105] Anode material 22 and cathode material 24 serve for the reversible storage of electrical energy and are the components of battery cells 17, which are to be recycled as so-called black mass from secondary batteries. For this purpose, a suitable starting material is provided from secondary batteries that have reached the end of their service life or are defective, as well as from other battery cells, precursors and production waste, from which black mass can be obtained.

[0106] Housing 18, battery core 19, anode 21, anode material 22, cathode 23, cathode material 24, separator 25, separator material 26, current collector 28 and current collector material 29 are components 31 of the battery cell 17.

[0107] Fig. 3 schematically shows a plant 32 which is operated via a control unit indicated at 33 in such a way that a suitable starting material is provided from secondary batteries 10 and other sources, from which the black mass is then obtained.

[0108] The system 32 has at its entrance a device 34 for receiving secondary batteries 10, which is depicted as a conveyor belt running largely through the system 10. A conveyor belt is only one possible embodiment; the device 34 could, for example, also include a worktable for receiving the secondary batteries 10 and robots or operators for transporting the secondary batteries 10. Therefore, the reference numeral 34 is used below to simplify the transport of material within the system 10.

[0109] The secondary batteries 10 are first placed in a device 35 for deep discharging them. This deep discharge is not strictly necessary for the new system 10, but is preferred for reasons of safe handling. The deeply discharged secondary batteries 10 are then transported to a separation device 36, where they are disassembled to the point that the battery cells 17 can be accessed. For this purpose, the other components of the secondary batteries 10, such as the battery housing 11, the electronic control unit 12, the casing 15, and the electrical connections 16, are separated from the battery cells 17.

[0110] This separation can also be done manually in some cases. However, robots and image processing systems can also be used if the separation is to be fully automated. The parts of the secondary batteries 10 cut off from the housings 11 can, for example, be automatically removed using vacuum grippers.

[0111] Advantageously, the removal process includes cutting and / or punching, preferably waterjet cutting and / or metal punching. Waterjet cutting has the advantage that the water used in the process can effectively suppress spontaneous combustion of the battery cells 17. Furthermore, a waterjet cutter allows the mechanical connections of the battery 10 housing 11 to be opened easily and quickly, and then the battery cell modules 14 to be separated from the other components of the battery 10 before the battery cell casings 15 are removed to expose the battery cells 17.

[0112] Arrow 37 indicates that these other components, which include, for example, metal parts and / or plastic parts, are removed and recycled elsewhere.

[0113] The battery cells 17 are then transported into an opening device 38, in which the casings 18 of at least some of the battery cells 17 are opened at least to the extent that an opening is created in the casing 18, providing a connection for liquid to the battery core 19. It is also possible for the battery core 19 to be completely separated from the casing 18 in the opening device 38. The casings 18 can then be cut into smaller pieces and recycled, as indicated by arrow 39. If the battery cells 17 do not have cylindrical casings 18, but rather prismatic casings, these casings are opened and / or removed from the battery core in a comparable manner.

[0114] If the battery cells 17 are pouch battery cells, in which the battery core is contained in a flat, non-metallic casing, these casings will be torn or cut open in the opening device.

[0115] A preferred embodiment of the opening device 38 for processing battery cells 17 with cylindrical housings 18 is described below in connection with Fig. 4.

[0116] Battery cells 17 from other sources can also be supplied to the opening device 38, as indicated by an arrow 40.

[0117] The opening device 38 exits a suitable starting material 41, which may contain components 31, here battery cells 17 with housing 18, battery cores 19 and housings 18 emptied thereof, parts of housings 18 and battery cells 17 with at least one opening in the housing 18.

[0118] The starting material 41 can be supplemented with intermediate products and production waste from other sources, indicated by an arrow 42, provided that black mass can also be obtained from them.

[0119] For the subsequent processing of the suitable starting material 41, it is irrelevant whether it is obtained only from secondary batteries 10 and / or battery cells 17 from other sources (arrow 40), and / or contains intermediate products and production waste from other sources (arrow 42).

[0120] In any case, the starting material 41 is “suitable” insofar as black mass can be obtained from it.

[0121] The starting material 41 then enters a device 43 for comminuting the starting material 41, more precisely for comminuting the battery cells 17 and components 31 of battery cells 17 contained therein, whereby at least the anode material 22, cathode material 24 and current collector material 29 are separated from each other.

[0122] The device 43 contains a trough 44 with electrically conductive liquid 45, which consists essentially of water. The starting material 41 is introduced into this liquid 45 and is pulverized there by shock waves.

[0123] A preferred embodiment of the device 43 utilizes electrohydraulic comminution, as described below in connection with Fig. 5.

[0124] By comminuting the starting material 41 in the device 43, different components 31 of the battery cells 17, battery cores 19, and any intermediate products and production waste 42 contained in the starting material 41 are separated and, if applicable, broken down into smaller fragments 50. In the mixture 46 resulting in the liquid 45, which is discharged from the device 43, these different components 31 are mostly separated from one another and are partly present as fragments 50, which are also referred to as particles or parts.

[0125] The liquid 45 with the mixture 46 distributed therein is fed by a suitable transfer device 47 into a device 48 for sorting the separated components and fragments and forms the essentially two-phase starting system 49 for the further process steps taking place in the device 48.

[0126] In the device 48, anode material 22 and cathode material 24 are essentially placed in a first container 51, thus forming black mass 52. The other components 54 are collected in one or more further containers 53, whereby for the sake of clarity only one further container 53 is shown.

[0127] These other components 54 include in particular housing (plastic, metal) 18, separator material (plastic, ceramic) 26 and current collector material (metal) 29. In particular the current collector material 29, but also housing 18 and separator material 26 can each be placed in a separate container 54.

[0128] Precursors for new electrode materials can then be obtained from the black mass 52 via chemical processing.

[0129] If liquid electrolyte 27 is present in the starting material 41, it does not enter one of the other containers 53, but initially remains in the liquid 45, in which it dissolves or mixes.

[0130] A preferred embodiment of the device 48 is described below in connection with Fig. 6.

[0131] Fig. 4 schematically shows an embodiment of the opening device 38 from Fig. 3. The opening device 38 comprises a battery receptacle 61 designed to fit the battery cell 17 and having a longitudinal direction 60, with a hollow cylindrical tube 62 having open end faces 63, 64 and a longitudinal slot 65 extending through the tube 62 from one end face 63, 64 to the other.

[0132] The tube 62 has a length indicated at 66 which is less than the length of the battery cell 17 indicated at 67, so that a battery cell 17 inserted into the battery receptacle 61 protrudes with its head 68 and its bottom 68 beyond the end faces 64 and 63 respectively of the battery receptacle 61.

[0133] After inserting the battery cell 27 into the battery holder 61, the head 68 and base 69 are removed along the dashed lines 70a, 70b and 70c with a punch 71 indicated above the battery holder 61; see also Fig. 4a.

[0134] The die 71 is equipped with three cutting blades 72, 73, 74. The cutting blades 72 and 73 cut off the bottom 69 along line 70a and the head 68 along line 70b of the battery cell 17 in a first and, if necessary, a second cut, creating openings 75, 76 in the housing 17, as shown in Fig. 5, which extend to the battery core 19 in the interior 20 of the housing 18. Because the cut or cuts through the housing 18 of the battery cell 17 are made close to the upper and / or lower edge of the housing 18, damage to the battery core 19 inside the housing 20 is avoided.

[0135] The precisely fitting battery holder 61 prevents deformation of the housing 18.

[0136] In a further cut, the punching knife 74 creates a lateral opening 77 in the casing 18 through the longitudinal slot 65 along the line 70c, also shown in Fig. 5, which also extends into the interior 20, but does not damage the cell nucleus 19.

[0137] In a next step, either the battery core 19 is ejected from the cut-up housing 18, which is still in the battery receptacle 61, or the battery cell 17, now provided with openings 75, 76, 77 in the housing 18, is completely ejected.

[0138] The opened battery cells 17 and / or battery cores 19 as well as the fragmented housings 18 and their parts, in particular the detached bottom 69 and the detached head 68, are then transferred as starting material 41 to the device 43 and crushed there.

[0139] It is also possible to separate the fragmented housings 18 and their parts from the starting material 41 from the opening device 38 and to send them for separate recycling; see arrow 39 in Fig. 3.

[0140] By shredding or comparable separation methods known from the prior art, the components of the battery cells are severely comminuted and compressed together to such an extent that they can only be separated from one another in subsequent processing steps with considerable time and energy expenditure. The result is a black mass 52 heavily contaminated with other components, in which the materials are also present as small fragments or flakes, which complicates further processing. In contrast, in the starting material 41 exiting the new opening device 38, the components are present in their original size and arrangement relative to one another due to the way in which the casings 18 are opened and, if necessary, the battery cores 19 are removed from them. The subsequent shredding and sorting therefore yields a much purer black mass 52, in which the separated components are often still in or almost in their original size.

[0141] This also reduces the time and energy required in the following device 43 shown in Fig. 5, in which the starting material 41 is now crushed electrohydraulically.

[0142] The openings 75, 76, 77 also make the subsequent electrohydraulic comminution more efficient, because the openings provide a fluid connection to the interior 20 of the housing 18, allowing the generated shock waves to penetrate the interior 20 more easily and exert their comminutionary effect there. The new process is thus more economical and ecological.

[0143] As discussed below in connection with Fig. 5, it is not necessary to provide the housing 18 of each battery cell 17 with openings 75, 76, 77.

[0144] The housing 18 of a certain number of battery cells 17, preferably the housing 18 of at least 20%, preferably at least 30%, particularly preferably at least 60%, most preferably at least 80%, in particular at least 95%, of the battery cells 17, in relation to the total quantity of battery cells 17, is therefore provided with at least one opening 75, 76, 77.

[0145] Figure 5 shows, as an example, only battery cells 17 with housings 18 in the starting material 41, in which openings 75, 76, and 77 are provided by the opening device 38. It is understood that battery cores 19, housings 18, and / or their parts, and / or precursors supplied from other sources, and / or production waste 42 may also be present. The tray 44 contains water with dissolved additives (e.g., lithium hydroxide and / or calcium carbonate) as an electrically conductive liquid 45, which improves the electrical conductivity. The starting material 41 is contained in the liquid 45. Two electrodes 81 and 82 protrude into the liquid, and the inner surface 83 of the tray 44 can also be used as an electrode.

[0146] A high electrical voltage is now applied to electrodes 81, 82, 83, generating a lightning discharge 84 that abruptly displaces a portion of the mass of the liquid 45, thus triggering a shock or mass wave that propagates through the liquid 45 and impacts the battery cells 17. The battery cells 17 are electrohydraulically separated into their individual components by a sequence of shock waves.

[0147] The generated mass waves, due to their different propagation speeds in different materials, create forces at the interfaces of the battery cell components 17, which drive the components of the battery cell 17 apart and separate them from one another. The advantage of electrohydraulic comminution is that the mass wave preferentially acts at the material boundaries and therefore separates the different materials more effectively than it comminutes them.

[0148] This results in the material fractions being significantly different from one another, making them easier and cleaner to separate. Additionally, underwater processing offers greater safety against ignition and the release of hazardous substances.

[0149] Electrohydraulic comminution can be carried out using parameters as specified in Table 1 below.

[0150] Volume of the tub: 301

[0151] Electrical capacitance 0.7 pF

[0152] Discharge voltage 25 to 40 kV

[0153] Energy per pulse: 219 to 560 J

[0154]

[0155] Pulse frequency 1 to 4 Hz

[0156] Table 1: Using the parameters specified in the table, an energy requirement of 0.7 to 2 kWh / kg of battery cells can result. The throughput can be up to 10 kg / h.

[0157] After a predetermined number of shock waves or time, the mixture 46 is found in the liquid 45, in which the different components 31 of the battery cells 17, battery cores 19, and possibly pre-products and production waste 42 contained in the starting material 41 are separated and possibly broken down into smaller fragments 50.

[0158] The electrohydraulic comminution separates the anode material 22 and cathode material 24 from the other components of the battery cells 17, such as the electrolyte 27, the separator 25, the current collectors 28, and, if present, the housing 18. The current collectors 28 and the separator 25 are delaminated in this process.

[0159] If liquid electrolyte 27 is present in the starting material 41, it dissolves in or mixes with the liquid 45, in which it may then decompose.

[0160] As an example, the function and effect of the device 43 were tested depending on the number of openings 75, 76, 77 provided in the opening device 38 in the housings 18 of the battery cells 17.

[0161] For each set of 30 battery cells 17 with a total mass of 1.76 kg, which either had no open casing 18, a casing 18 with only one opening 75 or 76, a casing 18 with two openings 75 and 76 or a completely removed casing 17, electrohydraulic comminution was carried out with the parameters specified in Table 1 until sufficient separation of the individual components of the respective battery cells 17 was achieved.

[0162] The results are shown in Table 2 below. Housing, number of electrical energy, battery cells, electrical pulses

[0163] without cutting 5500 3.3 kW with 1 parallel cut 2300 1.5 kW with 2 parallel cuts 2100 1.2 kW

[0164]

[0165] removed 700 0.7 kW

[0166] Table 2

[0167] The table above shows that cutting the casing 18 reduces the number of electrical pulses required, and thus also the electrical energy needed to achieve sufficient separation of the individual components of each battery cell 17. The lowest number of pulses and electrical energy are required when the casing 18 of the battery cells 17 is completely removed after making three cuts, so that only the battery cores 19 need to be crushed.

[0168] Fig. 6 shows intact battery cells 17 (here: 18650 battery cells) in the upper part and the components 31 of the battery cells 17 or the fragments 50 of the components 31 after electrohydraulic comminution in the lower part. In the lower part of Fig. 6, current collectors 28 or parts thereof, separated into copper flakes and aluminum flakes, are shown on the left, the black mass 52, i.e., the anode material 22 and cathode material 24, in the middle, and the other components on the right, which here consist of separator 25 or parts thereof and parts of the housings 18, i.e., steel housing, sealing ring, and so-called tabs welded to the current collectors 28, via which the poles 30 of the battery cells 17 are connected to the current collectors.

[0169] After the electrohydraulic comminution of the starting material 42 has been carried out in the device 43, the mixture 46 of various components 31 of battery cells 17, distributed in the liquid 45, is now present in the trough 44 as a starting system 49 for the subsequent sorting. This mixture 46 is now transferred by means of a suitable transfer device 47 into the device 48 shown schematically in Fig. 7 for sorting the components.

[0170] The device 48 comprises a tubular drum 87, preferably made of stainless steel V4A, which in Fig. 7 on the left has a lid 88 with an opening 89.

[0171] The horizontally oriented drum 87 also has a shell 91 in which pores 92 with a diameter of approximately 500 µm, indicated at 93, are located.

[0172] In drum 89, inserts in the form of wings are arranged for swirling and transporting the material taken up, which are not visible in Fig. 7 but are shown in Figs. 8 and 9.

[0173] The drum 89 is arranged to be rotatable about a horizontal axis 94, which is indicated by an arrow 95.

[0174] The starting system 49, i.e., the liquid 45 with the mixture 46 distributed therein, enters the drum 87 from the left through the opening 89 in Fig. 7 and is moved to the right by the rotation of the drum 87 about the axis 94 and the vanes. During this process, the smaller particles contained in the mixture 46, along with the liquid 45, enter a collection tray 96 located below the drum 87, while the larger particles are retained in the drum 87.

[0175] In this way, suspended particles from current collector 28 and separator 25, and possibly from housings 18, are separated from the black mass 52 and dissolved components in the liquid 45. The dissolved components include, in particular, liquid electrolyte 27, as well as salts and carbonates.

[0176] In this process, particles contained in the mixture are moved and washed in the rotating drum 87 using the wings, thereby improving the mixing and suspension of smaller particles or soluble substances.

[0177] In this way, a liquid phase referred to as process water97 collects in the collection tray 96, which contains the liquid 45 as well as suspended particles 50 of the black mass 52 and dissolved substances.

[0178] This process water 97 is conveyed by means of a feed pump 98 through pipelines 99 into a centrifuge 101 which can be rotated about a vertical axis 100, in which the black mass 52 is separated from the liquid 45 and the components dissolved therein and sorted into the first container 51.

[0179] The centrifuge 101 is preferably a hydrocyclone, i.e. a centrifugal separator.

[0180] The separated liquid 45 is pumped back into the drum 87 through pipes 103 using another pump 102.

[0181] The process water 97 returned from the centrifuge 101 to the drum 87 compensates for the liquid loss in the drum 87 during batch operation, so that the fragments 50 are washed and swirled several times, which improves the filter effect.

[0182] A drain valve 104 is arranged on the feed pump 102, which keeps the level of the process water 97 in the collection tray 96 approximately constant when the device 48 is operating in flow mode, i.e., when the starting system 49 is continuously fed through the opening 89.

[0183] The interaction of the two feed pumps 98 and 102 with the drain valve 104 regulates the level of the liquid 45 in the drum 87 and the level of the process water 97 in the collection tray 96.

[0184] When the device 48 operates in batch mode, process water 97 is returned to the drum 87 until the process water 97 is optically clear, which is monitored by a turbidity measurement.

[0185] If the process water 97 is sufficiently clear, the drain valve 104 is permanently opened, and all the liquid 45 in the drum 87 is directed through the pores 92 into the collection tray 96, from there into the centrifuge 101, and then via the pipes 103 to the drain valve 104, where it is discharged to the outside, stored, and, if necessary, further processed. A dry mass of heavy fragments remains in the drum 87, which is transported out of the drum 87 to the right by the vanes and collected in a container shown in Fig. 10.

[0186] When the device 48 operates in flow-through mode, process water 97 is continuously fed from the collection tray 96 into the centrifuge 101 and centrifuged there. The flow rate of process water 97 and the rotational speed of the centrifuge 101 are adjusted to ensure good purification even in flow-through mode.

[0187] The larger particles retained in drum 87 can be easily and quickly separated from each other based on their different densities.

[0188] For example, separators 25 made of plastic have a lower density than water and their particles float on the surface 105 of the liquid 45, from where they can be “skimmed off” using a skimmer.

[0189] The current collectors 28 and parts of the housings 18 have a higher density than water, so that their particles remain in the drum 87 after the particles of the separators 25 have been skimmed off, after the liquid 45 has left the drum 87 through the pores 92.

[0190] The particles sieved from the water can then be sorted into separate containers using a sorting machine with magnetic separation, eddy current sorting and sensor sorting.

[0191] The black mass 52 collects on an inner wall 106 of the centrifuge 101 and is then removed from the inner wall 106 in a suitable manner.

[0192] The individual fractions can be washed with process water before being sorted into separate containers.

[0193] In batch operation, after filling the starting system 49, the drum 87 can first be rotated for an initial period of 1 to 20 minutes at a speed of 0.5 rpm, and then for a second period of 1 to 15 minutes at a higher speed of 25 rpm. During the first period, the lighter fragments separate from the heavier fragments and float to the surface 105, from where they are skimmed off.

[0194] During the second period, the fragments are “washed” and swirled around due to the higher rotational speed, whereby fragments that are stuck together separate from each other and either leave the drum 7 with the process water 97 or are retained.

[0195] Fig. 8 shows a development of the shell 91 of the drum 87, showing a view of its inner surface 107, on which various vanes 108 are arranged at an angle 109 of 10° to a perpendicular 110 to the axis of rotation 94. Each vane 108 projects with its surface 111 towards the axis of rotation 94.

[0196] When the drum 87 rotates, the material inside it is moved along the axis of rotation 94 by the vanes 108 and mixed in the process. Depending on the direction of rotation of the drum 87 and / or the position of the angle of attack 109 to the left (positive angle of attack 109) or right (negative angle of attack) from the vertical 110, the material is transported to the left or right in Fig. 8.

[0197] Fig. 9 shows a view of the drum 87 in Fig. 7 from the right, but without the skimming device shown in Fig. 10. An exemplary vane 108 can be seen, the surface 111 of which is rotated relative to the axis of rotation 94.

[0198] Furthermore, Fig. 9 shows, by way of example, two spray nozzles 112, 113, which spray rinsing fluid 115 onto the jacket 91 from the outside and inside, respectively, in order to detach adhering fragments 50. The rinsing fluid 115 is generally process water 97 that has been recirculated via the feed pump 102.

[0199] Because the process water 97 is not only returned to the drum 87 via the feed pump 104, but is also used as rinsing fluid 115, the volume of the process water 97 discharged through the drain valve 104 and further treated is not unnecessarily increased beyond the volume of the liquid 45. This keeps the volume of the process water 97 to be treated as small as possible, which reduces the effort and costs of the treatment.

[0200] Fig. 10 shows a schematic side view of the drum 87 in longitudinal section. Visible is the liquid 45 inside the drum 87 with the fragments 50 distributed within it, of which the lighter ones float on the surface 105, while the heavier ones accumulate at the bottom on the inner surface 107 of the shell 91, as they cannot pass through the pores 92.

[0201] Inside the drum 87 is a skimming device 116, which has a conveyor belt 117 running obliquely upwards to the right, which projects from above through the surface 105 into the liquid 45 and moves along an arrow 118, thereby skimming the lighter fragments 50 from the surface 105 and transporting them out of the drum 87, where they fall into a container 119.

[0202] As described above in connection with Figs. 7 and 8, the wings 108 move heavy fragments 50, which accumulate on the inside 107 of the shell 91 of the drum 87, to the right out of the drum 87, where they fall into a container 120.

[0203] The following tables 3 to 5 describe the mass balance after electrohydraulic comminution according to Fig. 5 and sorting according to Fig. 7 for different types of battery cells 17.

[0204] The device 48 was operated in batch mode, which means that a specific quantity of mixture 46 was processed for each trial.

[0205] For this purpose, the specified quantity of mixture 46 was placed in drum 91, which was then rotated at a speed of 15 rpm (revolutions per minute). In this particular experiment, centrifuge 101 was a cyclone centrifuge operated at a speed of 2,500 rpm.

[0206] The experiment was terminated once mixture 46 was completely sorted. Mass Proportion Purity Input 1.76 kg

[0207] Black mass 0.79 kg 44.9 wt.% >90% Aluminum 0.11 kg 6.3% Mixed fraction Copper 0.17 kg 9.7% tion: >75% Separator 0.09 kg 5.1% -% Metals from the

[0208] 0.36 kg 20.5% >75% Housing

[0209] electrolyte in

[0210] 0.18 kg 10.2%

[0211] Process water - %

[0212]

[0213] Table 3: Mass balance for 30 cylindrical battery cells (type 18650)

[0214] Mass, proportion, purity, input: 2.4 kg, 100 wt.%

[0215] Black mass 1.0 kg 42 wt.% >90% >75% Aluminum 0.06 kg 2.5 wt.%

[0216] Copper 0.3 kg 12.5 wt.% >90% Mixed metal 0.5 kg 21 wt.% -% Separator 0.13 kg 5.4 wt.% -% Metals from Ge 0.3 kg 12.5 wt.% >70% housing

[0217] Electrolyte in the pro-%

[0218] 0.1 kg 4.0 l wt.%

[0219] cess water

[0220]

[0221] Table 4: Mass balance for 3 prismatic battery cells

[0222] Mass Percentage Purity Input 815 g 100%

[0223] Black mass 665 g 81.6 wt.% >90% Aluminum 35 g 4.3 wt.%

[0224]

[0225] Copper 50 g 6.1 wt.%

[0226] separator made of

[0227] 35 g 4.3% wt

[0228] plastic

[0229] Metals from casing 20 g 2.5 wt.%

[0230] sn

[0231] Electrolyte in the process water and

[0232] 1.2 wt.%

[0233] other return 10 g

[0234] stands

[0235]

[0236] Table 5: Mass balance for pouch cells

[0237] The impurity levels in the black mass after carrying out the process according to the invention were as follows:

[0238] 1.4 wt.% < copper < 3.8 wt.%

[0239] 1.1 wt.% < Aluminum < 2.6 wt.%

[0240] 0.5 wt.% < Iron < 1.6 wt.% (<0.05 wt.% for pouch with Al housing)

[0241] Reference symbol list

[0242] 10: Battery system / Secondary battery

[0243] 11: Battery housing of battery system / secondary battery

[0244] 12: electronic control

[0245] 14: Battery cell module

[0246] 15: Housing of battery cell module

[0247] 16: electrical connections

[0248] 17: Battery cell

[0249] 18: cylindrical housing of battery cell

[0250] 18a: Battery casing

[0251] 19: Battery core

[0252] 20: Interior of the cylindrical casing of the battery cell

[0253] 21: Anode

[0254] 22: Anode material

[0255] 23: Cathode

[0256] 24: Cathode material

[0257] 25: Separator (as electrolyte or for holding an electrolyte) 26: Separator material 27: Electrolyte

[0258] 28: Current collector

[0259] 29: Current collector material

[0260] 30: Pol

[0261] 31: Components of battery cell (cylindrical housing of battery cell, battery core, anode, anode material, cathode, cathode material, separator, separator material, current collector and / or current collector material)

[0262] 32: Annex

[0263] 33: Control unit

[0264] 34: Device for receiving battery system / secondary battery (e.g.

[0265] (Conveyor belt)

[0266] 35: Device for deep discharge

[0267] 36: Separation device for components of battery system / secondary battery (e.g. robot and / or tool hand)

[0268] 37: Arrow other components (i.e. battery casing of battery system / secondary battery, electronic control, battery cell module, casing of battery cell module and electrical connections) for other recycling

[0269] 38: Opening device for cylindrical housing of battery cell 39: Arrow cylindrical housing of battery cell recycled elsewhere 40: Supply of battery cell from other sources

[0270] 41: Starting material

[0271] 42: Pre-products and / or production waste

[0272] 43: Device for crushing raw material

[0273] 44: Bathtub

[0274] 45: Liquid

[0275] 46: Mixture; parts, particles, flakes, fragments

[0276] 47: Transfer device

[0277] 48: Sorting device

[0278] 49: two-phase starting system (essentially)

[0279] 50: Fragments of battery cell components

[0280] 51: first container

[0281] 52: Black mass

[0282] 53: additional container

[0283] 54: other components 60: longitudinal direction

[0284] 61: Battery compartment

[0285] 62: Pipe

[0286] 63: first front

[0287] 64: second front

[0288] 65: first longitudinal section

[0289] 66: Length of pipe

[0290] 67: Length of battery cell

[0291] 68: Head of battery cell

[0292] 69: Base of battery cell

[0293] 70a: dashed line

[0294] 70b: dashed line

[0295] 70c: dashed line

[0296] 71: Punch

[0297] 72: first die

[0298] 73: second die

[0299] 74: third cutting blade

[0300] 75: first opening

[0301] 76: second opening

[0302] 77: third opening

[0303] 81: High-voltage electrode

[0304] 82: High-voltage electrode

[0305] 83: Inside of bathtub

[0306] 84: Lightning discharge

[0307] 87: tubular drum, which can be cylindrical or conical 88: lid

[0308] 89: Opening

[0309] 91: Coat

[0310] 92: Pores

[0311] 93: Diameter

[0312] 94: horizontal axis of rotation

[0313] 95: Arrow

[0314] 96: Drip tray

[0315] 97: Process water

[0316] 98: Pump 99: Pipelines

[0317] 100 vertical axis

[0318] 101 Centrifuge - Hydrocyclone

[0319] 102 Pump

[0320] 103 pipelines

[0321] 104 Drain valve

[0322] 105 Surface area of ​​liquid in a tubular drum

[0323] 106 Inner wall of centrifuge - hydrocyclone

[0324] 107 Inside of coat

[0325] 108 wings

[0326] 109 Angle of attack

[0327] 110 Perpendicular to horizontal axis of rotation

[0328] 111 Area of ​​angle of attack

[0329] 112 first spray nozzle

[0330] 114 second spray nozzle

[0331] 115 rinsing fluid

[0332] 116 Skimming device

[0333] 117 Conveyor belt

[0334] 118 Arrow

[0335] 119 Containers for light fragments of battery cell components 120 Containers for heavy fragments of battery cell components

Claims

Fraunhofer Society...eV, Viridis Innovation GmbH P150453PC00 Patent claims 1. Method for obtaining black mass from a mixture of fragments of battery cell components, comprising the steps a) providing a starting system containing the mixture dispersed in a liquid, b) Filtering the starter system through a multi-pore filter device and collecting the filtered starter system as process water containing unfiltered fragments, c) Centrifuging the process water to separate the process water from the unfiltered fragments, and d) Transferring the fragments separated during centrifugation as black mass into a first container, wherein the pores have dimensions adapted to the dimensions of the fragments in the mixture such that at least 90%, preferably at least 95%, of the fragments of anode and / or cathode material contained in the starting system can pass through the pores.

2. Method according to the preceding claim, characterized in that the pores have a diameter of < 2 mm, preferably in the range of 0.01 mm to 1 mm, more preferably of approximately 0.5 mm.

3. A method according to any one of the preceding claims, characterized in that the filter device comprises a tubular drum with a horizontal axis of rotation and a shell in which the pores are arranged, and that the drum is rotated about the horizontal axis of rotation.

4. A method according to claim 3, characterized in that at least one vane is arranged inside the shell, and that when the drum is rotated, the liquid and the mixture distributed in it are transported in the direction of the axis of rotation and the fragments are loosened.

5. Method according to claim 3 or 4, characterized in that the drum is rotated in step b) at a speed between 0.1 and 100 rpm.

6. Method according to one of claims 3 to 5, characterized in that the filtering process in step b) has at least a first and a second duration, wherein the rotational speed of the drum during the first duration is different from the rotational speed of the drum during the second duration.

7. Method according to one of claims 3 to 6, characterized in that a skimming device is arranged in the drum which skims off fragments floating on top of the liquid in the drum and transports them out of the drum.

8. Method according to one of the preceding claims, characterized in that during or after step b) a rinsing fluid is sprayed onto the jacket from the inside and / or the outside, preferably under a pressure between 1.1 and 250 bar.

9. Method according to claim 8, characterized in that, after completion of step b), any fragments remaining in the drum are removed from the drum.

10. Method according to one of the preceding claims, characterized in that in step c) the process water is centrifuged, preferably at a speed between 200 and 5,000 rpm, until a predetermined turbidity level is reached, and the centrifuged process water is then returned to the drum as rinsing liquid.

11. Method according to one of the preceding claims, characterized in that in step a) a suitable starting material is provided which contains battery cells and / or components of battery cells, and that the starting material is crushed by shock waves to obtain the mixture of the fragments of the components.

12. Method according to claim 11, characterized in that in step a) an electrohydraulic comminution of the starting material suspended in an electrically conductive liquid is carried out, wherein a pulsed electrical voltage is applied to the liquid via at least two electrodes in order to generate the shock waves as lightning discharges, wherein the electrical voltage is preferably i) in the range of 20 to 240 kV; and / or ii) has a pulse frequency in the range of 0.1 to 200 Hz; and / or iii) causes a discharge that has an energy per electrode and per voltage pulse in the range of > 200 J.

13. Method according to one of the preceding claims, characterized in that the starting material is obtained by providing battery cells with housings and providing the housings with at least one opening.

14. Method according to the preceding claim, characterized in that the at least one opening is produced by at least one cut through the housing.

15. Device for obtaining black mass from a mixture of fragments of battery cell components, comprising a porous filter device for receiving and filtering a starting system containing the mixture dispersed in liquid, a collection device for collecting the filtered start-up system as process water containing unfiltered fragments, and a separation system to separate process water and unfiltered fragments from each other and to transfer the separated fragments as black mass into a first container, wherein the pores have dimensions adapted to the dimensions of the fragments in the mixture such that at least 90%, preferably at least 95%, of the fragments of anode and / or cathode material contained in the starting system can pass through the pores.

16. Device according to claim 15, characterized in that the pores have a diameter of < 2 mm, preferably in the range of 0.01 mm to 1 mm, more preferably of approximately 0.5 mm.

17. Device according to one of claims 15 or 16, characterized in that the filter device has a tubular drum with a horizontal axis of rotation and a shell in which the pores are arranged, and that the drum is rotatably driven about the horizontal axis of rotation.

18. Device according to claim 17, characterized in that at least one wing is arranged inside the casing, which has an angle of attack perpendicular to the axis of rotation of the drum, which is in the range of +10° to -10° to the axis of rotation.

19. Device according to claim 17 or 18, characterized in that a skimming device is arranged in the drum to skim off fragments floating on top of the liquid in the drum and transport them out of the drum.

20. Device according to any one of claims 17 to 19, characterized in that the filter device has spray nozzles to spray a rinsing liquid onto the jacket.

21. Device according to one of claims 15 to 20, characterized in that the separation system has a centrifuge which is connected to the filter device via a pipe system in order to direct centrifuged process water into the filter device as rinsing liquid.

22. Plant for the production of black mass from a suitable starting material, with a) a device for crushing the starting material with shock waves in order to produce a starting system from a mixture of fragments of battery cell components dispersed in a liquid, b) the device according to one of claims 15 to 21, for sorting separated anode and cathode material as black mass into a first container, and c) a control unit for controlling the plant.

23. Plant according to claim 22, characterized in that the device for comminuting the starting material comprises a trough for receiving the starting material in an electrically conductive liquid and at least two electrodes, wherein the control unit is configured to apply a pulsed electrical voltage to the liquid via the at least two electrodes, which is preferably i) in the range of 20 to 240 kV; and / or ii) has a pulse frequency in the range of 0.1 to 200 Hz; and / or iii) causes a discharge that has an energy per electrode and per voltage pulse in the range of > 200 J.

24. System according to one of claims 22 or 23, characterized in that it comprises a device for receiving secondary batteries and a disconnecting device, and the control unit is configured to cause the disconnecting device to disconnect battery cell modules and / or battery cells contained in the received secondary batteries from other components of the secondary battery.

25. System according to one of claims 22 to 24, characterized in that it has an opening device for producing at least one opening in a housing of battery cells, wherein the openings between the interior of the housing and the exterior of the housing establish a fluid-conducting connection, wherein the control unit is configured to cause the opening device to produce at least one such opening in the housing of the battery cells.

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