METHOD AND DEVICE FOR DISAGGREGATION OF PARTICLE COMPOSITES

Abstract

The present invention relates to a method for the disaggregation of particle composites, in which particle composites comprising or consisting of electrode coating material particles bound with at least one binder are introduced into a process medium, the particle composites introduced into the process medium are subjected to at least one shock wave treatment, whereby the particle composites at least partially disaggregate and disaggregated electrode coating material particles are obtained, and the disaggregated electrode coating material particles are separated from the process medium.In addition, the present invention also relates to a device for disaggregating particle composites, comprising a reactor with a device for generating shock waves, a container for a process medium in which the reactor is at least partially arranged, at least one filling device for filling the reactor with particle composites comprising or consisting of electrode coating material particles bound with at least one binder, and at least one first separation device for separating disaggregated electrode coating material particles from the process medium.

Description

[0001] The present invention relates to a method for the disaggregation of particle composites, in which particle composites comprising or consisting of electrode coating material particles bound with at least one binder are introduced into a process medium, the particle composites introduced into the process medium are subjected to at least one shock wave treatment, whereby the particle composites at least partially disaggregate and disaggregated electrode coating material particles are obtained, and the disaggregated electrode coating material particles are separated from the process medium.In addition, the present invention also relates to a device for disaggregating particle composites, comprising a reactor with a device for generating shock waves, a container for a process medium in which the reactor is at least partially arranged, at least one filling device for filling the reactor with particle composites comprising or consisting of electrode coating material particles bound with at least one binder, and at least one first separation device for separating disaggregated electrode coating material particles from the process medium.

[0002] Energy storage devices, such as lithium-ion batteries, and energy converters contain significant amounts of valuable and sometimes even critical raw materials such as Li, Ni, Co, or graphite. Furthermore, the production of their materials, especially their electrode materials, is associated with significant costs, emissions, and resource and energy consumption. Efficient recycling of these energy storage devices and energy converters is therefore of enormous importance and one of the greatest challenges for sustainable electromobility and the energy transition. Early classification of the various materials they contain is a fundamental prerequisite for this.

[0003] There are already established processes for the separation into the main components: metal fractions (e.g., Fe, Al, Cu), organic compounds (e.g., separators, electrolyte solvents), and black mass (a mixture of various, partially bonded electrode materials). These processes are essentially based on mechanical comminution and subsequent classification. There are also implemented solutions for the separation of electrode production rejects into metal foils (Al or Cu) and black mass (electrode coating fragments) (see EP 2 975 686 A1). However, the separation into the individual electrode materials still represents a major technical problem. This separation would bring significant advantages to conventional pyro- and hydrometallurgical recycling routes and would also enable even more efficient direct recycling of functional materials.

[0004] For example, a reduced carbon content (graphite, conductive carbon black, binder) of the black mass in the pyrometallurgical processes would CO 2 -Emissions and simultaneously prevent the carbon from influencing process conditions and thus metal recovery and process efficiency. In hydrometallurgical processes, reducing the carbon content means fewer process chemicals are required, which also saves costs and resources and reduces negative environmental impacts. Most importantly, however, obtaining the various energy storage and energy conversion materials as intact, functional materials with high purity would enable direct recycling, which would save enormous amounts of emissions, energy consumption, and process resource consumption in the synthesis of new energy storage and energy conversion materials.

[0005] The conductive additives and parts of the binder can be thermally removed at temperatures from 400 °C, but this requires high energy consumption, additional CO / CO 2 Emissions and potentially hazardous substances such as HF (due to the decomposition of PVDF binders) are generated, preventing the materials from being recycled. Thermally removing the graphite would require even higher temperatures, which would have an even greater negative impact on emissions as well as energy and resource efficiency. Furthermore, thermal treatment can cause significant damage to the remaining electrode material—particularly in nickel-rich NMC materials.

[0006] Various methods have been investigated for the structure-preserving separation or concentration of the various electrode materials, such as flotation or centrifugation (see Yu Zhang Yaqun He et al., Journal of Cleaner Production, Volume 202, 2018, pages 736-747). However, their separation efficiency is limited by the fact that the electrode particles to be separated are still partially bound together by binders in the black mass and thus exist as larger fragments of active material particles and conductive carbon black particles. This prevents complete separation and complicates the determination of suitable process parameters.

[0007] To disaggregate and debind the electrode particles for subsequent flotation, the thermal removal of conductive additives and binder particles under an oxygen atmosphere at temperatures of 400 °C (see Ruiting Zhan et al., ASC Sustainable Chem. Eng. 2021, 9,1, 531-540) or above 700 °C was investigated (see Younghun Kim et al., Resources Processing 2004, Volume 51, Issue 1, Pages 3-7). However, these processes have the disadvantages described above regarding efficiency and emissions. During treatment at 400 °C, parts of the PVDF binder remained intact, and even treatment above 700 °C did not allow complete separation of the cathode active material particles (metal oxides) from the anode active material particles (graphite). In addition, the structure of the cathode active material (e.g., LCO or NMC) can be destroyed at high temperatures.

[0008] Another option for separating aggregates bonded with binder is mechanical treatment by grinding or attrition. However, studies have shown that this can break up the active materials and, for example, destroy the lamellar graphite structure (see Jladong Yu et al., Grinding flotation, Separation and Purificat-Ion Technology, Volume 190, 2018, pages 45-52), or that aggregates are not completely separated and the binder is not completely removed (see A. Vanderbruggen et al., Minerals 2022, 12, 72). In particular, breaking up the particles creates additional inhomogeneities, which can negatively impact the separation efficiency, e.g., of conductive carbon black and graphite. Furthermore, the destroyed particles are of limited use for direct recycling.

[0009] Chemical binder removal can, in turn, lead to further contamination and thus further environmental pollution. Binder removal using Fenton reagents has revealed iron-containing particle deposits that require complex removal using additional chemicals or negatively impact the surface properties of the particles and thus their flotation behavior (see Jiadong Yu et al., Powder Technology, Volume 315, 2017, pages 139-146). Furthermore, it is unclear whether the chemicals fully reach the areas bonded with binder in larger aggregates.

[0010] Based on this, it was the object of the present invention to provide a method and a device with which particle composites comprising or consisting of electrode coating material particles bound with a binder can be disaggregated as non-destructively and as completely as possible.

[0011] This object is achieved with respect to a method for disaggregating particle composites having the features of patent claim 1 and with respect to a device for disaggregating particle composites having the features of patent claim 12. The respective dependent patent claims represent advantageous developments.

[0012] According to the invention, a method for the disaggregation of particle composites is provided, in which a) particle composites comprising or consisting of electrode coating material particles bound with (at least one) binder are introduced into a process medium, b) the particle composites introduced into the process medium are subjected to (at least) one shock wave treatment, whereby the particle composites at least partially disaggregate and disaggregated electrode coating material particles are obtained, and c) the disaggregated electrode coating material particles are separated from the process medium.

[0013] In step a) of the process according to the invention, particle composites are introduced into a (liquid) process medium. The process medium can also be referred to as the reactor medium. For example, water, dihydrolevoglucosenone, propylene carbonate or a mixture of several of these can be used as the process medium. The particle composites comprise or consist of electrode coating material particles and (at least one) binder, wherein the electrode coating material particles are bound (e.g., glued) by the binder. The particle composites preferably originate from used and / or disposed of or recycled electrodes, which originate, for example, from used and / or disposed of or recycled energy storage devices (e.g., batteries) and / or energy converters (e.g., fuel cells). For example, the particle composites can originate from coatings of such electrodes. The particle composites can also be referred to as particle aggregates.Electrode coating material particles can be understood to mean particles made of one or more materials that are used in and / or on electrodes (or electrode coatings), such as active material, capacitor material, catalyst material, (electrode coating) additives (e.g. conductive carbon black, carbon nanotubes, pore formers, and / or metal particles), and / or solid electrolytes. The (at least one) binder can be a binder or binder mixture commonly used in electrodes (for binding electrode material). The (at least one) binder is preferably selected from the group consisting of sodium carboxymethylcellulose, styrene-butadiene rubber, polyvinylidene fluoride, polyacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, sodium alginate, and mixtures thereof.

[0014] The particle composites can, for example, contain or consist of black mass. Black mass can be understood as a mixture obtained during battery recycling and consisting of electrode coating fragments (separated from electrode substrates and / or electrode substrate fragments) and optionally impurities (e.g., aluminum (Al), copper (Cu), iron (Fe), separator shreds, and / or electrolyte residues).

[0015] An electrode typically comprises an electrode substrate and at least one electrode coating arranged on the electrode substrate. The at least one electrode coating can be arranged on a front side and / or on a back side of the electrode substrate. The electrode substrate can preferably be an electrode current collector.

[0016] In step b) of the method according to the invention, the particle composites introduced into the process medium in step a) are subjected to at least one shock wave treatment. The at least one shock wave treatment at least partially disaggregates the particle composites, obtaining disaggregated electrode coating material particles. In other words, the particle composites (comprising the electrode coating material particles and the at least one binder) are at least partially separated into individual (disaggregated) electrode coating material particles by the at least one shock wave treatment, i.e. the bond in the particle composites provided by the at least one binder is at least partially dissolved. The disaggregated electrode coating material particles can comprise the binder or parts of the binder, i.e.The binder or parts of the binder may be bound to the disaggregated electrode coating material particles. This may be the case, in particular, if the at least one binder is not (or only partially) soluble in the process medium. Alternatively, the disaggregated electrode coating material particles may also be free of binder, i.e., they may not comprise any binder bound to them. This may be the case, in particular, if the at least one binder is (at least partially) soluble in the process medium.

[0017] Preferably, the electrode coating material particles are at least partially debindered by the at least one shock wave treatment, ie parts of the at least one binder are completely separated from the electrode coating material particles.

[0018] Preferably, the particle composites are (essentially) completely disaggregated by the at least one shock wave treatment, whereby disaggregated electrode coating material particles are obtained. “Essentially completely disaggregated” can be understood here as meaning that at least 90% by weight, preferably at least 95% by weight, particularly preferably at least 97% by weight, very particularly preferably at least 99% by weight, of the particle composites, based on the total weight of the particle composites, are disaggregated. The weight percentage can be determined, for example, by weighing, for example by weighing the particle composites before the at least one shock wave treatment and the (non-disaggregated) particle composites after the at least one shock wave treatment, and comparing the difference with the weight of the particle composites before the at least one shock wave treatment.

[0019] Shock wave treatment can be understood as treatment with shock waves. Shock waves can also be referred to as shock waves or bang waves. A shock wave can be understood as a pressure wave in which parts of the medium (as the pressure wave propagates), e.g. the process medium, are moved faster than the speed of sound in the medium. Preferably, during shock wave treatment at least one shock wave is generated by means of at least one shock discharge, wherein the at least one shock discharge is preferably generated by at least one high-voltage pulse. Particularly preferably, during shock wave treatment shock waves are generated by means of shock discharges, wherein the shock discharges are preferably generated by high-voltage pulses.

[0020] In step c) of the process according to the invention, the disaggregated electrode coating material particles obtained in step b) are separated from the process medium. The separation can be carried out, for example, by centrifugation, by sieving, by filtration, by sedimentation and discharge (e.g. by means of at least one conveyor belt), or by combinations thereof. If the disaggregated electrode coating material particles comprise the binder or parts of the binder, i.e. if the binder or parts of the binder are bound to the disaggregated electrode coating material particles, the binder bound to the disaggregated electrode coating material particles or the parts of the binder bound to the disaggregated electrode coating material particles are preferably separated from the process medium together with the disaggregated electrode coating material particles in step c).

[0021] By means of the method according to the invention, the particle composites comprising or consisting of electrode coating material particles bound with (at least one) binder can be disaggregated almost or completely non-destructively and (essentially) completely.

[0022] The solution for the almost or completely non-destructive disaggregation of particle composites is shock wave treatment in a (liquid) process medium. Relatively low energies (relative to shock wave processes) can be used. The (liquid) process medium is preferably, but not necessarily, a solvent for the existing binder and can preferably be heated for a better dissolving effect.

[0023] The advantage of shock waves compared to ultrasound is that the pressure amplitudes are particularly large, which enables a stronger force to be exerted on the particle composites to be separated.

[0024] The method according to the invention enables the classification of various electrode coating materials, for example into active materials (cathode active material, e.g., NMC and / or LFP; and / or anode active material, e.g., graphite and / or LTO), capacitor materials, catalyst materials, solid electrolytes, and / or (electrode coating) additives (e.g., conductive carbon black, carbon nanotubes, pore formers, and / or metal particles), to be carried out more efficiently and effectively. Classification processes such as flotation or centrifugation require starting particles that are as non-sticky as possible in order to separate them, for example, according to their density and particle size.

[0025] Disaggregation (and optional debinding) occurs without significant damage to the active material and / or capacitor material (e.g., no significant particle breakup, no serious surface contamination, and no thermal decomposition) and offers the optional possibility of recycling the catalyst materials, solid electrolytes, and / or (electrode coating) additives, as well as the binder. Furthermore, disaggregation (and optional debinding) of the electrode coating material particles can preferably be combined with detachment from the electrode substrates (preferably electrode current collectors) of the electrodes (e.g., Al or Cu) to reduce process steps.

[0026] The process does not require high temperatures (e.g., 400 °C or higher), no critical chemicals such as NMP, and can preferably be operated continuously (e.g., by integrating a sieve into the reactor). For increased sustainability, the process medium can preferably be recycled multiple times and subsequently reused after treatment. By selecting the process medium and process parameters (e.g., energy input, treatment duration), the process can be flexibly adapted to different input fractions and requirements.

[0027] A preferred variant of the method according to the invention is characterized in that during the shock wave treatment one or more shock waves are generated by means of one or more shock discharges, wherein the shock discharges are preferably generated by one or more high-voltage pulses, which are preferably - have / have a frequency in the range of 0.1 Hz to 500 Hz, preferably from 1 Hz to 50 Hz, and / or - have / have a working voltage in the range of 10 kV to 100 kV, preferably from 20 kV to 75 kV, particularly preferably from 30 kV to 50 kV, and / or - has / have a discharge energy in the range from 1 J to 12000 J, preferably from 1 J to 1000 J, particularly preferably from 1 J to 600 J, very particularly preferably 1 J to 300 J, in particular 1 J to 100 J, for example 1 J to 50 J.

[0028] In these areas, a particularly advantageous disaggregation of the particle composites can be achieved, resulting in particularly minimal damage and a particularly comprehensive disaggregation of the particles. A comparatively low energy has proven ideal for this purpose – high enough to break up the aggregates, but low enough not to damage the particles. The use of a low discharge energy thus leads to a finer separation of the particle composites, less damage to the particles, and energy savings. A discharge energy in the range of 1 J to 300 J, in particular 1 J to 100 J, for example 1 J to 50 J, is particularly preferred.

[0029] A further preferred variant of the method according to the invention is characterized in that - the process medium contains or consists of at least one solvent and optionally at least one (process medium) additive, wherein the at least one solvent is selected from the group consisting of water, dihydrolevoglucosenone, propylene carbonate, and mixtures thereof, wherein the at least one solvent is particularly preferably water, and / or - the at least one binder is selected from the group consisting of sodium carboxymethylcellulose, styrene-butadiene rubber, polyvinylidene fluoride, polyacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, sodium alginate, and mixtures thereof, and / or - the at least one binder dissolves at least partially in the process medium, wherein preferably the process medium with the at least one binder dissolved therein is subjected to a separation process for separating the at least one binder from the process medium, which separation process is preferably selected from the group consisting of distillation, filtration, and combinations thereof, wherein particularly preferably the process medium is heated.

[0030] The at least one (process medium) additive optionally contained in the process medium is preferably selected from the group consisting of acids and bases, such as acetic acid (C 2 H 4 O 2 or CH 3 COOH), citric acid (C 6 H 8 O 7 ), ENT 3 , LiOH, and / or Ca(OH) 2(for adjusting pH values, avoiding undesirable reactions / leaching, preventing HF formation and / or neutralizing HF), film formers such as vinylene carbonate, and mixtures thereof.

[0031] The separation process for separating the at least one binder from the process medium can preferably be carried out before, during, and / or after step c). Preferably, the process medium with the dissolved binder can be circulated several times (in a recirculation process) or used for an extended period (in a continuous process), whereby the binder can be removed from the process medium after a certain saturation of the process medium with dissolved binder, e.g., by evaporation and condensation of the process medium. This enables both material recycling of the binder and sustainable reuse of the process medium.

[0032] By using a binder that dissolves in the process medium, a much easier separation of the binder from the electrode coating material particles can be achieved, thereby significantly shortening the process. Furthermore, by using a binder that dissolves in the process medium, a simple, rapid, and (essentially) complete decoating of the particle composites from electrode substrates can be achieved, provided that particle composites arranged on electrode substrates are used. This results in fewer disruptive reactions and less contamination of the disaggregated electrode coating material particles with material from the electrode substrates.

[0033] According to a further preferred variant of the method according to the invention, - in step c) the disaggregated electrode coating material particles are separated from the process medium by means of a separation process selected from the group consisting of centrifugation, sieving, filtration, sedimentation and discharge (e.g. by means of at least one conveyor belt), as well as combinations thereof, and / or - in step c) the disaggregated electrode coating material particles are first separated from the particle composites (i.e. a portion of the particle composites which are not or not yet disaggregated) and then separated from the process medium, wherein the separation of the disaggregated electrode coating material particles from the particle composites is preferably carried out using at least one separation method selected from the group consisting of centrifugation, sieving, filtration, sedimentation and discharge (e.g. by means of at least one conveyor belt), as well as combinations thereof.

[0034] A further preferred variant of the method according to the invention is characterized in that in step c) the disaggregated electrode coating material particles are first separated from the particle composites (i.e. a portion of the particle composites that are not or not yet disaggregated) by means of at least one first separation process, which is preferably selected from the group consisting of centrifugation, sieving, filtration, sedimentation and discharge (e.g. by means of at least one conveyor belt), and combinations thereof, and then the disaggregated electrode coating material particles separated from the particle composites are separated from the process medium by means of at least one second separation process, which is preferably selected from the group consisting of centrifugation, sieving, filtration, sedimentation and discharge (e.g. by means of at least one conveyor belt), and combinations thereof.

[0035] A further preferred variant of the method according to the invention is characterized in that - step b) is carried out after step a), step c) is carried out after step b), and after step c) the sequence of steps a) to c) is repeated once or several times, wherein the process medium is circulated and the process medium used in each step a) carried out after a step c) is at least partly the process medium from which the disaggregated electrode coating material particles were separated in the previous step c), or - the process is carried out continuously (and steps a) to c) are carried out at least partly simultaneously), wherein the process medium remains in the same container during the process, wherein the particle composites of electrode coating material particles bound with the at least one binder are continuously introduced into the process medium located in the container, the disaggregated electrode coating material particles are continuously separated from the particle composites, and the disaggregated electrode coating material particles separated from the particle composites are continuously separated from the process medium located in the container, wherein preferably • the continuous separation of the disaggregated electrode coating material particles from the particle composites is carried out by means of at least one sieve and / or filter, and / or • the continuous separation of the disaggregated electrode coating material particles separated from the particle composites from the process medium in the container takes place via at least one conveyor belt.

[0036] According to a further preferred variant of the process according to the invention, the disaggregated electrode coating material particles are, after step c) - debinding, wherein the debinding is preferably carried out by a process selected from the group consisting of Soxhlet processes, treatment with solvents and / or supercritical fluids, heating, and combinations thereof, and / or - sorted, wherein the sorting is preferably carried out by a process selected from the group consisting of sieving, wet sieving, filtering, centrifuging, centrifugal separation, heavy sludge separation, flotation, sedimentation, magnetic separation, eddy current separation, air classification and combinations thereof.

[0037] Preferably, the particle composites are fragments of electrode coatings which comprise or consist of the electrode coating material particles bound with binder.

[0038] A further preferred variant of the method according to the invention is characterized in that the electrode coating material particles - (battery) active material particles and / or capacitor material particles, and / or - catalyst particles, preferably coated carbon particles and / or - (Electrode coating) additive particles, preferably selected from the group consisting of conductive carbon black particles, carbon nanotubes, pore formers, metal particles, and mixtures thereof, and / or - comprise or consist of solid electrolyte particles.

[0039] The (battery) active material particles and / or capacitor material particles preferably comprise or consist of at least one material which is selected from the group consisting of - Anode active materials for lithium-ion batteries, preferably graphite (C), silicon (Si), silicon suboxides (SiO x ), lithium (Li), graphite / silicon composites (Si-C), graphite / silicon suboxide composites (SiO x -C), lithium titanate (Li 4 Ti 5 O 12 , LTO), hard carbon (hard carbon), - Cathode active materials for lithium-ion batteries, preferably lithium cobalt(III) oxide (LiCoO 2 , LCO), lithium-nickel-cobalt-aluminum oxide (Li(Ni,Co,Al)O 2 , NCA), lithium-nickel-manganese-cobalt oxide (Li(Ni,Mn,Co)O 2 , NMC), lithium manganese (III,IV) oxide (LiMn 2 O 4 , LMO), lithium iron phosphate (LiFePO 4 , LFP), - Anode active materials for sodium-ion batteries, preferably carbon-containing materials such as hard carbon (non-graphitic carbon), graphene (including doping if necessary); metals / metal alloys such as Sn, Sb or SnSb; transition metal oxides / sulfides such as Na 4 TisO 12 ; Organics such as Na 2 C 10 H 2 O 4 , - Cathode active materials for sodium-ion batteries, preferably polyanionic compounds such as sodium iron phosphate (NaFePO 4 , NFP) and sodium vanadium phosphate (Na3V2(PO4)3), layered oxides such as sodium manganese oxide (Na x MnO 2 ), sodium iron manganese oxide (Na 2 / 3 Fe 1 / 2 Mn 1 / 2 O 2 ) and sodium nickel manganese oxide (Na 2 / 3 No 1 / 4 Mn 3 / 4 O 2 ), organic compounds such as Na 2 C 6 O 6 , - Anode and cathode active materials for solid-state batteries, preferably graphite (C), silicon (Si), silicon suboxides (SiO x ), lithium (Li), graphite / silicon composites (Si-C), graphite / silicon suboxide composites (SiO x -C), lithium titanate (Li 4 Ti 5 O 12 , LTO), hard carbon, lithium cobalt(III) oxide (LiCoO 2 , LCO), lithium-nickel-cobalt-aluminum oxide (Li(Ni,Co,Al)O 2 , NCA), lithium-nickel-manganese-cobalt oxide (Li(Ni,Mn,Co)O 2 , NMC), lithium manganese (III,IV) oxide (LiMn 2 O 4 , LMO), lithium iron phosphate (LiFePO 4 , LFP); and additionally a solid electrolyte (anolyte or catholyte), - Anode active materials for lithium-sulfur batteries, preferably carbon, silicon or tin-containing materials, lithium (Li), C-Li compounds, Si-Li compounds, Si-C-Li compounds, Sn-C-Li compounds, metal compounds, - Cathode active materials for lithium-sulfur batteries, preferably sulfur (S), lithium sulfide (Li 2 S), sulfur / carbon composites, sulfur / metal oxide composites or sulfur / conductive polymer composites, modifications with MOFs (Metal Organic Frameworks), - Electrode materials for supercapacitors (same on both sides), preferably activated carbon (AC), activated carbon fiber (AFC), carbide-derived carbon (CDC), carbon aerogel, graphite (graphene) and carbon nanotubes (CNTs), - Electrode materials for gas diffusion electrodes and / or catalyst layers of metal-air batteries such as zinc-air or lithium-air batteries (here cathode), of fuel cells or of electrolyzers, preferably (porous) carbons and / or catalysts (coated thereon or in mixture) made of precious metals such as platinum, ruthenium, iridium and rhenium, of transition metals from the group consisting of titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, ruthenium, rhodium, palladium, osmium, iridium and platinum or of metal oxides such as tin oxide, zinc oxide, titanium oxide, aluminum oxide, silver oxide and manganese dioxide (manganese dioxide and carbon are often used for zinc-air batteries) - and mixtures thereof.

[0040] Solid electrolytes are used, particularly in solid-state batteries, in both anodes and cathodes. In anodes, they are called anolytes, and in cathodes, catholytes. Such solid electrolytes can also be non-particulate. These electrolytes can also be polymers that fill the pores of the particulate electrodes. In the latter case, the electrolytes certainly also have a certain binding effect. For example, PMMA counts as a binder and, when combined with a conductive salt, also serves as a gel electrolyte.

[0041] A further preferred variant of the method according to the invention is characterized in that - the particle composites • electrode coatings and / or electrode coating fragments from pure electrodes, and / or • about black mass, and / or - in step a) no housings and / or housing fragments of energy storage devices and / or energy converters are introduced into the process medium.

[0042] A further preferred variant of the method according to the invention is characterized in that the particle composites are electrode coatings and / or electrode coating fragments of single-type electrodes. The single-type electrodes are preferably electrodes that - are exclusively cathodes, or - are exclusively anodes, or - Cathodes and anodes have the same composition, with the electrodes being, for example, components of supercapacitors or catalyst layers on membranes of fuel cells.

[0043] The pure electrodes are particularly preferably electrodes that have the same composition.

[0044] Single-variety electrodes, e.g. separate anode or cathode foils, can be obtained, for example, by using corresponding or appropriately sorted electrode production rejects as input material or, for example, by dismantling energy storage devices and / or energy converters, e.g. battery cells.

[0045] The resulting disaggregated electrode coating material particles can generally be reused more effectively if they originate from single-type electrodes (or single-type electrode coatings or fragments thereof). In contrast, particles from non-single-type electrodes must first be separated, which is complex and time-consuming, e.g., by flotation, in order to be used for direct recycling or to be processed more efficiently. By using electrode coatings and / or electrode coating fragments from single-type electrodes, pure fractions can be easily obtained that can be used immediately (or after relatively simple and rapid separation steps) for direct recycling. Furthermore, significantly higher purities can be achieved.The upstream sorting of the electrodes is simpler and generates better purities than the downstream sorting of the individual disaggregated electrode coating material particles.

[0046] Furthermore, the use of electrode coatings and / or electrode coating fragments from single-type electrodes also allows the process to be carried out more quickly and the duration of the at least one shock wave treatment to be shortened, since the parameters of the at least one shock wave treatment can be better tailored to a specific electrode type, so that both the disaggregation of the electrode coating material particles and a possible stripping of electrode substrates (preferably electrode current collectors), if particle composites arranged on electrode substrates are used, proceed more quickly. This ultimately also results in less contamination of the disaggregated electrode coating material particles with material from the electrode substrates.

[0047] The particle composites preferably originate from used and / or disposed or recycled energy storage devices (e.g. batteries) and / or energy converters (e.g. fuel cells).

[0048] A further preferred variant of the method according to the invention is characterized in that the particle composites - to • electrode coatings separated from (and isolated from) electrode substrates (preferably electrode current collectors), and / or • electrode coating fragments separated from (and isolated from) electrode substrates (preferably electrode current collectors) and / or electrode substrates (preferably electrode current collector fragments), or - solidified electrode coating pastes, or - to • electrode coatings arranged on electrode substrates (preferably electrode current collectors), and / or • electrode coating fragments arranged on electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments) of single-variety electrodes and / or of electrodes each comprising at least one binder that is at least partially soluble in the process medium (or the at least one binder that is at least partially soluble in the process medium), or - are mixtures of these.

[0049] In this embodiment, either no electrode substrates at all or only very specific electrode substrates (namely, electrode substrates of single-type electrodes and / or of electrodes each comprising a binder that is at least partially soluble in the process medium) are introduced into the process medium. In this way, the purity of the resulting disaggregated electrode coating material particles can be increased.

[0050] With regard to purity, it must first be considered that the material of the electrode substrates can contaminate the disaggregated electrode coating material particles during the at least one shock wave treatment. For example, metal contained in the electrode substrates, such as aluminum or copper, can lead to deposits on the disaggregated electrode coating material particles, particularly in the form of metal oxides or metal hydroxides (e.g., aluminum hydroxide). When using electrode coatings separated from electrode substrates, and / or electrode coating fragments separated from electrode substrates and / or electrode substrate fragments, as well as when using solidified electrode coating pastes, no electrode substrates (or fragments thereof) are introduced into the process medium, so that corresponding contamination can be avoided.

[0051] When using electrode coatings arranged on electrode substrates and / or electrode coating fragments arranged on electrode substrates and / or electrode substrate fragments of single-variety electrodes and / or electrodes each comprising a binder that is at least partially soluble in the process medium, although in principle electrode substrates (or fragments thereof) are introduced into the process medium, in these special cases a high purity of the disaggregated electrode coating material particles can still be achieved in a simple manner. Thus, both in the case of the use of electrode coatings (orBoth when using single-material electrodes (or fragments thereof) and when using a binder soluble in the process medium, a significantly faster detachment of the electrode coating material particles from the electrode substrates can be achieved, so that the at least one shock wave treatment can be carried out with such a short duration that there is no or only very minimal contamination of the electrode coating material particles by the material of the electrode substrates. Furthermore, when using electrode coatings (or fragments thereof) from single-material electrodes, the contaminants can be removed more easily and effectively, since only identical or similar contaminants are present and not mixtures of different contaminants.

[0052] Electrode substrates (preferably electrode current collectors) with electrode coatings arranged thereon can also be referred to as electrodes or as coated electrode substrates (preferably electrode current collectors).

[0053] Preferably, the electrode substrates may be electrode current collectors, particularly preferably electrode foils.

[0054] The electrode substrates (preferably electrode current collectors) are preferably selected from the group consisting of metal foils, preferably aluminum foils (e.g. for cathode), copper foils (e.g. for anode); metal meshes, preferably nickel meshes; metal foams; carbon current collectors; polymer current collectors; fiber current collectors; membranes, e.g. from fuel cells; and combinations thereof.

[0055] Solidified electrode coating pastes are electrode coating materials that were not applied to an electrode substrate, but rather solidified while not on an electrode substrate. These solidified electrode coating pastes arise as rejects and / or residues during the production of electrode coating pastes used to produce electrode coatings. Electrode coating pastes are thus precursors of electrode coatings; during the production of electrodes, such electrode coating pastes are applied to electrode substrates and solidified to form electrode coatings.

[0056] If the particle composites are at least partly - electrode coatings arranged on electrode substrates (preferably electrode current collectors), and / or - electrode coating fragments arranged on electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments), the electrode coatings and / or electrode coating fragments are at least partially separated from the electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments) by the shock wave treatment, and in the process de-coated electrode substrates (preferably electrode current collectors) and / or de-coated electrode substrate fragments (preferably electrode current collector fragments) are obtained, wherein in addition the particle composites are at least partially disaggregated by the shock wave treatment, and in the process disaggregated electrode coating material particles are obtained.

[0057] A further preferred variant of the method according to the invention is characterized in that the particle composites - were obtained thereby, or - (within the method according to the invention) are obtained before step a) by removing the coating from coated electrode substrates (preferably electrode current collectors) and / or fragments of coated electrode substrates (preferably electrode current collectors) (preferably by means of milling and / or pressure wave treatment), whereby a mixture of electrode substrate fragments (preferably electrode current collector fragments) and the particle composites was / are obtained, and the particle composites were / are separated (preferably by means of sieving) from the electrode substrate fragments (preferably electrode current collector fragments) and optionally were / are comminuted. In this case, it is preferred that the coated electrode substrates (preferably electrode current collectors) and / or fragments of coated electrode substrates (preferably electrode current collectors) - through • dismantling energy storage devices and / or energy converters, and / or • the crushing of energy storage devices and / or energy converters and subsequent separation of the fragments obtained by crushing were obtained, or - (within the process according to the invention) before step a) by • dismantling energy storage devices and / or energy converters, and / or • the crushing of energy storage devices and / or energy converters and subsequent separation of the fragments obtained by crushing - can be won.

[0058] In this preferred variant, only particle composites that have been separated from electrode substrates (preferably electrode current collectors) or their fragments and are thus present separated from electrode substrates (preferably electrode current collectors) or their fragments are introduced into the process medium. Therefore, no electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments) are introduced into the process medium. Furthermore, no housings and / or housing fragments of energy storage devices and / or energy converters are introduced into the process medium.

[0059] A further preferred variant of the method according to the invention is characterized in that the particle composites - were obtained thereby, or - (within the method according to the invention) before step a) are obtained by dismantling energy storage devices and / or energy converters, whereby electrodes are obtained, and the electrodes are subjected to a sorting process in which the particle composites comprising - pure electrodes, and / or - Electrodes, each comprising at least one binder which is at least partially soluble in the process medium (or the at least one binder which is soluble in the at least one process medium), were / are obtained by separating all remaining electrodes, wherein the obtained electrodes were / are optionally crushed.

[0060] In this preferred variant, only particle composites of specific electrodes are introduced into the process medium, which are still arranged on electrode substrates (preferably electrode current collectors) or fragments thereof, wherein these specific electrodes are single-variety electrodes and / or electrodes each comprising a binder that is at least partially soluble in the process medium. Therefore, only electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments) of these specific electrodes are introduced into the process medium. Furthermore, no housings and / or housing fragments of energy storage devices and / or energy converters are introduced into the process medium.

[0061] A further preferred variant of the process according to the invention is characterized in that in step a) only - Particle composites that • were obtained thereby, or • (within the method according to the invention) are obtained before step a) by removing the coating from coated electrode substrates (preferably electrode current collectors) and / or fragments of coated electrode substrates (preferably electrode current collectors) (preferably by means of milling and / or pressure wave treatment), whereby a mixture of electrode substrate fragments (preferably electrode current collector fragments) and the particle composites was / is obtained, and the particle composites were / are separated (preferably by means of sieving) from the electrode substrates (preferably electrode current collector fragments) and optionally were / are comminuted, whereby the coated electrode substrates (preferably electrode current collectors) and / or fragments of coated electrode substrates (preferably electrode current collectors) are preferably • through • dismantling energy storage devices and / or energy converters, and / or • the crushing of energy storage devices and / or energy converters and subsequent separation of the fragments obtained by crushing were obtained, or • (within the method according to the invention) before step a) by • dismantling energy storage devices and / or energy converters, and / or • the crushing of energy storage devices and / or energy converters and subsequent separation of the fragments obtained by crushing be obtained, and / or - Particle composites that • were obtained thereby, or • (within the method according to the invention) before step a) are obtained by dismantling energy storage devices and / or energy converters, whereby electrodes were / are obtained, and the electrodes were / are subjected to a sorting process in which the particle composites comprising • pure electrodes, and / or • Electrodes, each comprising a binder that is at least partially soluble in the process medium, were / are obtained by separating all remaining electrodes, wherein the resulting electrodes were / are optionally crushed, and / or - Particle composites that have arisen as rejects in the form of electrode coatings and / or electrode coating fragments during the manufacture of electrodes, energy storage devices and / or energy converters, and / or - Particle composites that have arisen as rejects in the form of electrodes during the production of electrodes, energy storage devices and / or energy converters and have subsequently been / are subjected to a sorting process in which the particle composites have comprehensive • pure electrodes, and / or • Electrodes, each comprising at least one binder that is at least partially soluble in the process medium, were / are obtained by separating all remaining electrodes, wherein the resulting electrodes were / are optionally crushed, and / or - particle composites that have arisen as rejects and / or residues in the form of solidified electrode coating pastes during the production of electrode coating pastes, and / or - Black mass introduced into the process medium.

[0062] In this preferred variant, only - particle composites that are separate from electrode substrates (preferably electrode current collectors) or fragments thereof, and / or - Particle composites of specific electrodes arranged on electrode substrates (preferably electrode current collectors) or fragments thereof, wherein these specific electrodes are single-type electrodes and / or electrodes each comprising a binder that is at least partially soluble in the process medium, are introduced into the process medium. Therefore, in this preferred variant, either - no electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments) are introduced into the process medium, or - only electrode substrates (electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments) of • pure electrodes, and / or • Electrodes, each comprising a binder that is at least partially soluble in the process medium, are introduced into the process medium.

[0063] In addition, in this preferred variant, no housings and / or housing fragments of energy storage devices and / or energy converters are introduced into the process medium.

[0064] By not introducing any electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments) into the process medium or by introducing only electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments) of single-variety electrodes and / or electrodes each comprising a binder that is at least partially soluble in the process medium into the process medium, the purity of the resulting disaggregated electrode coating material particles can be increased.

[0065] By avoiding the introduction of housings and / or housing fragments of energy storage devices and / or energy converters into the process medium, the purity of the resulting disaggregated electrode coating material particles can also be increased. Furthermore, introducing particle composites into the process medium that have already been extracted and separated from the housings of energy storage devices and / or energy converters can achieve significant advantages, as the process can be carried out much more quickly and, in addition, significantly lower energies can be used for at least one shock wave treatment.If complete energy storage devices and / or energy converters were introduced into the process medium, at least one shock wave treatment would have to achieve not only the disaggregation of the particles and the decoating of the electrode substrates (preferably electrode current collectors), but also the simultaneous opening of the housing of the energy storage device and / or energy converter. This would have the disadvantage that comparatively high pulse energies would have to be used and longer treatment times would be required, whereas the particle disaggregation and decoating of the electrode substrates can be achieved with significantly lower energies and comparatively shorter treatment times after prior housing opening and separation. This ultimately also leads to more selective comminution and / or decomposition.Better separation of the materials from one another with reduced damage to the particles and reduced chemical reaction of the electrode substrates, which in turn increases the purity of the particles. Furthermore, by opening the housing beforehand, large portions of the electrolyte can be removed before the shock wave treatment for particle disaggregation / de-coating of the electrode substrates, thus preventing unwanted reactions or contamination of the process medium during at least one shock wave treatment.

[0066] The treatment of particle composites that have already been removed from and separated from the housings of energy storage devices and / or energy converters is therefore advantageous compared to the treatment of intact energy storage devices and / or energy converters. This allows for lower pulse energies, shorter treatment times, and prevents interfering substances such as the housing and the electrolyte from being completely or partially removed from the process medium during at least one shock wave treatment. This leads to better and more non-destructive separation of the materials, reduced contamination by crushed components (e.g., Al, Cu) or reaction products (e.g., aluminum or fluorine compounds), and time and energy savings.

[0067] It is therefore a particularly preferred variant of the method according to the invention that the particle composites (which are introduced into the process medium in step a)) are particle composites that are separated from the housings and / or housing fragments of energy storage devices and / or energy converters. In other words, it is particularly preferred that (in step a)) no housings and / or housing fragments of energy storage devices and / or energy converters are introduced into the process medium.

[0068] A further preferred variant of the process according to the invention is characterized in that in (step a)) exclusively - particle composites that are separate from electrode substrates (preferably electrode current collectors) or fragments thereof, and / or - particle composites of certain electrodes which are still arranged on electrode substrates (preferably electrode current collectors) or the fragments thereof, wherein these certain electrodes are single-variety electrodes and / or electrodes which each comprise a binder which is at least partially soluble in the process medium, are introduced into the process medium.

[0069] A further preferred variant of the process according to the invention is characterized in that (in step a)) either - no electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments) are introduced into the process medium, or - only electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments) of • pure electrodes, and / or • Electrodes, each comprising a binder that is at least partially soluble in the process medium, - are introduced into the process medium.

[0070] A further preferred variant of the method according to the invention is characterized in that - step b) is carried out after step a), step c) is carried out after step b), and after step c) the sequence of steps a) to c) is repeated once or several times, wherein the process medium is circulated and the process medium used in each step a) carried out after a step c) is at least partially the process medium from which the disaggregated electrode coating material particles were separated in the previous step c), wherein the at least one binder dissolves at least partially in the process medium, and wherein the process medium with the at least one binder dissolved therein is subjected to a separation process for separating the at least one binder from the process medium after the process medium has been circulated several times, or - the process is carried out continuously (and steps a) to c) are carried out at least partially simultaneously), wherein the process medium remains in the same container during the process, wherein the particle composites of the electrode coating material particles bound with the at least one binder are continuously introduced into the process medium present in the container, the disaggregated electrode coating material particles are continuously separated from the particle composites, and the disaggregated electrode coating material particles separated from the particle composites are continuously separated from the process medium present in the container, wherein the at least one binder dissolves at least partially in the process medium, and wherein the process medium with the at least one binder dissolved therein is subjected to a separation process for separating the at least one binder from the process medium,after the process has been carried out continuously for at least 5 minutes, preferably at least 20 minutes, more preferably at least 1 hour, most preferably at least 2 hours. ,

[0071] A further preferred variant of the method according to the invention is characterized in that the particle composites are at least partially - electrode coatings arranged on electrode substrates (preferably electrode current collectors), and / or - electrode coating fragments arranged on electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments), wherein the (coated) electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments) are at least partially stripped of their coating by the at least one shock wave treatment, and stripped electrode substrates (preferably electrode current collectors) and / or stripped electrode substrate fragments (preferably electrode current collector fragments) are obtained, and the at least one shock wave treatment at least partially disaggregates the particle composites, and disaggregated electrode coating material particles are obtained. In this preferred variant, the particle composites are in the form of (orwithin) electrode coatings and / or electrode coating fragments are present which are arranged on electrode substrates (preferably electrode current collectors) and / or on electrode substrate fragments (preferably electrode current collector fragments). In other words, in this preferred variant, in step a), electrode substrates (or complete electrodes) coated with at least one electrode coating and / or fragments of electrode substrates (or fragments of complete electrodes) coated with at least one electrode coating are introduced into the process medium, wherein the at least one electrode coating contains or consists of the particle composites. The electrode substrates and / or electrode substrate fragments are decoated by the shock wave treatment. This means that the at least one electrode coating is removed from the electrode substrates or the electrode substrate fragments.In this way, stripped electrode substrates and / or stripped electrode substrate fragments are obtained. Furthermore, the shock wave treatment also at least partially disaggregates the particle composites, yielding disaggregated electrode coating material particles.

[0072] Electrode substrates (preferably electrode current collectors) with electrode coatings arranged thereon can also be referred to as electrodes or as coated electrode substrates (preferably electrode current collectors).

[0073] It is preferred that - the stripped electrode substrates (preferably electrode current collectors) and / or stripped electrode substrate fragments (preferably electrode current collector fragments) are separated from the process medium, preferably by means of a separation process selected from the group consisting of centrifugation, sieving, filtration, sedimentation and discharge (e.g. by means of at least one conveyor belt), as well as combinations thereof, and / or - the disaggregated electrode coating material particles are separated from the process medium, preferably by means of a separation process selected from the group consisting of centrifugation, sieving, filtration, sedimentation and discharge (e.g. by means of at least one conveyor belt), as well as combinations thereof, and / or - the stripped electrode substrates (preferably electrode current collectors) and / or stripped electrode substrate fragments (preferably electrode current collector fragments) are separated from the disaggregated electrode coating material particles, preferably by means of a separation process selected from the group consisting of sieving, washing, and combinations thereof.

[0074] According to a particularly preferred variant of the method according to the invention, the at least one shock wave treatment - the electrode substrates (preferably electrode current collectors) and / or electrode substrate fragments (preferably electrode current collector fragments) are stripped and stripped electrode substrates (preferably electrode current collectors) and / or stripped electrode substrate fragments (preferably electrode current collector fragments) are obtained, - the particle composites are at least partially disaggregated and disaggregated electrode coating material particles are obtained, and - the electrode coating material particles are at least partially debound.

[0075] The present invention also relates to a device for disaggregating particle composites, comprising a reactor with a device for generating shock waves, a container for a process medium in which the reactor is at least partially arranged, at least one filling device for filling the reactor with particle composites comprising or consisting of electrode coating material particles bound (e.g. glued) with at least one binder, and at least one first separation device for separating disaggregated electrode coating material particles from the process medium.

[0076] The device according to the invention is preferably a device for disaggregating particle composites using the method according to the invention for disaggregating particle composites. In other words, the device according to the invention is preferably suitable for carrying out the method according to the invention.

[0077] A preferred embodiment of the device according to the invention is characterized in that - the device for generating shock waves is suitable for generating shock waves by means of one or more shock discharges (or is suitable for generating shock waves by means of one or more shock discharges), wherein the shock discharge(s) are preferably generated by one or more high-voltage pulse(s), which is / are preferably • has / have a frequency in the range of 0.1 Hz to 500 Hz, preferably from 1 Hz to 50 Hz, and / or • have / have a working voltage in the range of 10 kV to 100 kV, preferably from 20 kV to 75 kV, particularly preferably from 30 kV to 50 kV, and / or • has / have a discharge energy in the range from 1J to 12000 J, preferably from 1J to 1000 J, particularly preferably from 1J to 600 J, very particularly preferably 1J to 300 J, in particular 1J to 100 J, for example 1J to 50 J, and / or - the at least one filling device is at least one filling device for filling, preferably continuously filling, the reactor with particle composites comprising or consisting of electrode coating material particles bound with at least one binder, wherein the at least one filling device is preferably at least one (first) conveyor belt, and / or - the at least one first separation device is at least one separation device for separating, preferably continuously separating, disaggregated electrode coating material particles separated from the particle composites from the process medium, wherein the at least one first separation device is preferably at least one (second) conveyor belt, at least one sieve, and / or at least one filter, particularly preferably at least one (second) conveyor belt.

[0078] A further preferred embodiment of the device according to the invention is characterized in that the device additionally - at least one second separation device for separating, preferably continuously separating, the disaggregated electrode coating material particles from the particle composites, wherein the at least one second separation device is preferably at least one sieve and / or at least one filter, wherein the at least one sieve and / or the at least one filter particularly preferably has a perforated orMesh size of at most 5 mm, preferably at most 1 mm, particularly preferably at most 50 µm, and / or at least one third separation device for separating stripped electrode substrates (preferably electrode current collectors) and / or stripped electrode substrate fragments (preferably electrode current collector fragments) from the process medium, wherein the at least one third separation device is preferably at least one (third) conveyor belt, at least one sieve, and / or at least one filter, particularly preferably at least one sieve, or. - at least one combined (second) separation device for separating, preferably continuously separating, the disaggregated electrode coating material particles from the particle composites (as well as from stripped electrode substrates and / or electrode substrate fragments) and for separating, preferably continuously separating, stripped electrode substrates (preferably electrode current collectors) and / or stripped electrode substrate fragments (preferably electrode current collector fragments) from the process medium, wherein the at least one combined separation device is preferably at least one (third) conveyor belt with at least one integrated sieve, wherein the at least one integrated sieve particularly preferably has a hole or mesh width of at most 5 mm, preferably at most 1 mm, particularly preferably at most 50 µm.

[0079] A further preferred embodiment of the device according to the invention is characterized in that - the at least one filling device is at least one (first) conveyor belt (for continuously filling the reactor with particle composites comprising or consisting of electrode coating material particles bound with at least one binder), wherein the at least one (first) conveyor belt is preferably arranged above the reactor and / or above the container for the process medium, and / or - the at least one first separation device is at least one (second) conveyor belt (for continuously separating disaggregated electrode coating material particles separated from the particle composites from the process medium), wherein the at least one (second) conveyor belt is preferably arranged at least partially below the reactor and / or at least partially in the container for the process medium, and / or - the device additionally comprises at least one second separation device for continuously separating the disaggregated electrode coating material particles from the particle composites, wherein the at least one second separation device is preferably at least one sieve and / or at least one filter, wherein the at least one sieve and / or the at least one filter is particularly preferably • has a hole or mesh size of at most 5 mm, preferably at most 1 mm, particularly preferably at most 50 µm, and / or • is formed as part of a bottom of the reactor, or the device additionally comprises at least one combined (second) separation device for continuously separating the disaggregated electrode coating material particles from the particle composites (as well as from stripped electrode substrates and / or electrode substrate fragments) and for continuously separating stripped electrode substrates (preferably electrode current collectors) and / or stripped electrode substrate fragments (preferably electrode current collector fragments) from the process medium, wherein the at least one combined separation device is preferably at least one conveyor belt with at least one integrated sieve, wherein particularly preferably • the at least one integrated sieve has a hole or mesh size of at most 5 mm, preferably at most 1 mm, particularly preferably at most 50 µm, and / or • at least one (third) conveyor belt is formed as part of a bottom of the reactor.

[0080] Preferably, the method according to the invention is carried out with the device according to the invention.

[0081] The method and / or the device according to the invention can be used in particular for the disaggregation (and optional debinding) of electrode coating material particles for conventional metallurgical battery recycling and for direct battery recycling, and optionally also for the debinding of polymer-bonded magnets, unsintered binder jetting production rejects and other polymer-bonded particles.

[0082] The present invention will be explained in more detail with reference to the following figures and examples, without limiting it to the specific embodiments and parameters shown here. Example 1

[0083] Fig. 1 shows the process diagram of an exemplary variant of the method according to the invention. The diagram relates to the disaggregation of particle composites consisting of electrode coating material particles bound with a binder, wherein the particle composites are electrode coating fragments separated from electrode current collectors and / or electrode current collector fragments or black mass. The electrode coating fragments are introduced into a process medium (e.g., water) and treated with shock waves generated by means of shock discharges. The frequency of the high-voltage pulses that generate the shock discharges is, for example, in the range from 1 Hz to 50 Hz. The operating voltage is, for example, in the range from 10 kV to 100 kV, preferably from 20 kV to 75 kV, particularly preferably from 30 kV to 50 kV. The discharge energy is, for example,in the range from 1 J to 12,000 J, preferably from 1 J to 1,000 J, particularly preferably from 1 J to 600 J, very particularly preferably 1 J to 300 J, in particular 1 J to 100 J, for example 1 J to 50 J. After the shock wave treatment, the electrode coating material particles are largely or even completely detached from one another and can be separated from the process medium by simple separation processes such as centrifugation, sieving and / or filtration. The process medium can be recycled and used for the shock wave treatment of further electrode coating fragments. The disaggregated electrode coating material particles can optionally be additionally debindered (e.g. using the Soxhlet process) and offer the best conditions for this due to the exposed binder sites. They can then be used for optimized separation processes (e.g. graphite / conductive soot removal) and / or direct recycling.

[0084] Instead of circulating the process medium, a sieve and / or filter can also be integrated into the reactor of the shock wave system to continuously remove the disaggregated electrode particles. Depending on the requirements profile and particle types, sieve mesh sizes of, for example, 50 µm or smaller are ideal for this purpose. The sieved material can be removed via a conveyor belt, for example, and fresh material can be continuously replenished. This allows the treatment efficiency to be further optimized and a continuous process to be implemented. Example 2

[0085] Fig. 2 shows a further exemplary variant of the method according to the invention, which comprises the same steps as the exemplary variant according to embodiment 1. In addition, the electrode coating fragments used are previously obtained by stripping electrodes or coated electrode current collectors (ie electrode current collectors with an electrode coating arranged thereon), whereby a mixture of electrode current collector fragments and electrode coating fragments is obtained, and the electrode coating fragments are separated from the electrode current collector fragments.

[0086] Shown in Fig. 2 thus the entire process chain from coated electrode current collectors to the disaggregated electrode coating material particles. First, the electrode coating (consisting of the electrode particles bound with a binder or binding agent) is removed from the electrode current collectors (e.g. Al or Cu). This can be achieved using mechanical processes such as grinding and sieving or using pressure waves (ultrasonic or shock waves) followed by classification. During shock wave treatment, it should be noted that the aluminum partially decomposes to form aluminum hydroxide. The aluminum hydroxide then deposits on the electrode particles and contaminates them. Downstream chemical steps can be used for removal, such as treatment with NaOH, which generates further impurities and can damage the particles.A mechanical treatment for decoating followed by shock wave treatment for disaggregation is therefore the preferred solution, which can be implemented completely continuously. The mechanical treatment can be carried out (similarly) as described in EP 2 975 686 A1, if necessary with different screen sizes than the 200 µm described therein.

[0087] The processing of the electrode coating fragments, in particular the disaggregation of the particle composites, can be carried out according to the descriptions in Example 1. Example 3

[0088] Fig. Figure 3 shows another exemplary variant of the process according to the invention. In contrast to the variant according to Example 2, a process medium is used here that dissolves the binder or binding agent. For example, this is water when using CMC (carboxymethylcellulose), SBR (styrene-butadiene rubber), or mixtures of CMC and SBR as the binder.

[0089] In contrast to embodiment 2, the binder is not only exposed by disaggregation of the particles, but also dissolves in the process medium. The process medium can be heated to improve solubility. The separated, disaggregated electrode particles are therefore binder-free and can be more easily separated in a subsequent process and directly recycled. The process medium with the dissolved binder can preferably be recycled several times. After a certain saturation with dissolved binder, the binder can be removed from the process medium, for example, by evaporation and condensation. This enables both material recycling of the binder and sustainable reuse of the process medium.

[0090] All further process steps can be carried out as in (or analogously to) embodiment 1 or 2. Example 4

[0091] Fig. Figure 4 shows a further exemplary variant of the method according to the invention. Shown is a modification of the method described in embodiment 3 and in Fig. 3, whereby no prior decoating of the electrodes or the coated electrode current collectors (i.e. prior to introduction into the process medium) takes place, but instead the electrodes or the coated electrode current collectors (i.e. the electrode current collectors with the electrode coating arranged thereon) are introduced directly into the process medium. In other words, the particle composites that are introduced into the process medium are thus electrode coatings arranged on electrode current collectors. During the shock wave treatment, the coated electrode current collectors are then additionally decoated, so that ultimately this decoating, disaggregation and debinding take place together in the same shock wave treatment. For this purpose, a suitable process medium (e.g.a medium that dissolves the binder or does not attack aluminum as strongly), a suitable plant technology (e.g. continuous particle discharge through an integrated sieve in the reactor) and / or suitable process parameters (e.g. low pulse energy) must be used.

[0092] The further steps can be carried out as in (or analogously to) embodiment 3. Example 5

[0093] Fig. 5a and Fig. 5b show a simplified representation of an exemplary embodiment of the device according to the invention, wherein in Fig. 5b additionally shows the implementation of an exemplary variant of the method according to the invention. The device comprises a reactor 1 with a device (not shown) for generating shock waves, a container (not shown) for a process medium 2, in which the reactor 1 is partially arranged, a filling device 3 for continuously filling the reactor with particle composites comprising or consisting of electrode coating material particles bound with at least one binder, a second separation device 5 for continuously separating disaggregated electrode coating material particles 8 from the particle composites, and a first separation device 4 for continuously separating the disaggregated electrode coating material particles separated from the particle composites from the process medium 2.The second separation device 5 is a sieve or filter formed as part of a bottom of the reactor 1. The filling device 3 is a first conveyor belt arranged above the reactor 1. The first separation device 4 is a second conveyor belt arranged partially below the reactor 1 and partially in the container for the process medium 2.

[0094] In Fig. 5a and in Fig. In Figure 5b, the process medium 2 is shown with dotted lines / hatching, with the upper limit of the process medium being shown with a horizontal dotted line.

[0095] In the Fig. In the exemplary variant of the method according to the invention shown in Figure 5b, particle composites comprising or consisting of electrode coating material particles bound with at least one binder are introduced into the process medium 2 using the filling device 3, wherein the particle composites are electrode coating fragments 7 separated from electrode substrates and / or electrode substrate fragments. The particle composites introduced into the process medium 2 are subjected to at least one shock wave treatment, whereby the particle composites disaggregate and disaggregated electrode coating material particles 8 are obtained. During the shock wave treatment, a plurality of shock waves 9 are generated by means of a plurality of shock discharges (using the device for generating shock waves, not shown). The frequency of the high-voltage pulses that generate the shock discharges is, for example, in the range from 1 Hz to 50 Hz.The working voltage is, for example, in the range from 10 kV to 100 kV, preferably from 20 kV to 75 kV, particularly preferably from 30 kV to 50 kV. The discharge energy is, for example, in the range from 1 J to 12,000 J, preferably from 1 J to 1,000 J, particularly preferably from 1 J to 600 J, very particularly preferably from 1 J to 300 J, in particular from 1 J to 100 J, for example from 1 J to 50 J. The disaggregated electrode coating material particles 8 are then first separated from the particle composites using the second separation device 5 and then separated from the process medium 2 using the first separation device 4. Example 6

[0096] Fig. 6 shows a simplified representation of a further exemplary embodiment of the device according to the invention and a further exemplary variant of the method according to the invention. The device comprises a reactor 1 with a device (not shown) for generating shock waves, a container (not shown) for a process medium 2, in which the reactor 1 is partially arranged, a filling device 3 for continuously filling the reactor with particle composites comprising or consisting of electrode coating material particles bound with at least one binder, and a first separation device 4 for continuously separating the disaggregated electrode coating material particles separated from the particle composites from the process medium 2. The filling device 3 is a first conveyor belt arranged above the reactor 1.

[0097] In contrast to the method described in Example 5 and in Fig. 5a and Fig. 5b, the exemplary device shown here comprises a combined separation device 6 for continuously separating the disaggregated electrode coating material particles 8 from the particle composites (as well as from stripped electrode substrates 11 and / or electrode substrate fragments) and for continuously separating stripped electrode substrates 11 (and / or electrode substrate fragments) from the process medium 2. The at least one combined separation device 6 is a conveyor belt with an integrated sieve.

[0098] In Fig. 6, the process medium 2 is shown with dotted lines / hatching, with the upper limit of the process medium being shown with a horizontal dotted line.

[0099] In the Fig. In the exemplary variant of the method according to the invention shown in Figure 6, particle composites comprising or consisting of electrode coating material particles bound with at least one binder are introduced into the process medium 2 by means of the filling device 3, whereby - in contrast to the Fig. 5b - the particle composites are electrode coatings 10 arranged on electrode substrates 11. The particle composites introduced into the process medium 2 are subjected to at least one shock wave treatment, whereby the electrode substrates 11 are stripped of their coatings, thereby obtaining stripped electrode substrates 11 (and / or electrode substrate fragments), and the electrode coatings 10 are at least partially disaggregated, thereby obtaining disaggregated electrode coating material particles 8. During the shock wave treatment, a plurality of shock waves 9 are generated by means of a plurality of shock discharges (using the device for generating shock waves, not shown). The frequency of the high-voltage pulses that generate the shock discharges is, for example, in the range from 1 Hz to 50 Hz. The operating voltage is, for example, in the range from 10 kV to 100 kV, preferably from 20 kV to 75 kV, particularly preferably from 30 kV to 50 kV.The discharge energy is, for example, in the range from 1J to 12000 J, preferably from 1J to 1000 J, particularly preferably from 1J to 600 J, very particularly preferably 1J to 300 J, in particular 1J to 100 J, for example 1J to 50 J.

[0100] The combined separation device 6 then separates the disaggregated electrode coating material particles 8 from the particle composites (as well as from the stripped electrode substrates 11 and / or electrode substrate fragments) and separates the stripped electrode substrates 11 (and / or electrode substrate fragments) from the process medium 2, wherein the disaggregated electrode coating material particles 8 are also separated from the process medium 2 with the aid of the first separation device 4. Example 7

[0101] Particle composites from lithium-ion batteries were prepared and introduced into water as the process medium. The particle composites introduced into the water were treated with shock waves generated by means of shock discharges, with the shock discharges being generated by means of high-voltage pulses. The frequency of the high-voltage pulses was in the range of 1 Hz to 50 Hz. The working voltage of the high-voltage pulses was in the range of 30 kV to 50 kV. The discharge energy of the high-voltage pulses was in the range of 1 J to 600 J, preferably 1 J to 300 J, more preferably 1 J to 100 J, and most preferably 1 J to 50 J. After the shock wave treatment, the resulting disaggregated electrode coating material particles were separated from the process medium.

[0102] Fig. Figure 7 shows an SEM image of the obtained disaggregated electrode coating material particles.

[0103] As in Fig.As can be seen in Figure 7, the obtained disaggregated electrode coating material particles are essentially undamaged and essentially completely disaggregated. QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] EP 2 975 686 A1 [0003, 0086] Cited non-patent literature

[0000] Yu Zhang Yaqun He et al., Journal of Cleaner Production, Volume 202, 2018, Pages 736-747

[0006] Ruiting Zhan et al., ASC Sustainable Chem. Eng. 2021, 9.1, 531-540

[0007] Younghun Kim et al., Resources Processing 2004, Volume 51, Issue 1, Pages 3-7

[0007] Jladong Yu et al., Grinding flotation, Separation and Purificat-Ion Technology, Volume 190, 2018, Pages 45-52

[0008] A. Vanderbruggen et al., Minerals 2022, 12, 72

[0008] Jiadong Yu et al., Powder Technology, Volume 315, 2017, Pages 139-146

[0009]

Claims

[1] Process for the disaggregation of particle composites, in which a) particle composites comprising or consisting of electrode coating material particles bound with at least one binder are introduced into a process medium (2), b) the particle composites introduced into the process medium (2) are subjected to at least one shock wave treatment, whereby the particle composites at least partially disaggregate and disaggregated electrode coating material particles (8) are obtained, and c) the disaggregated electrode coating material particles (8) are separated from the process medium (2). [2] Method according to the preceding claim, characterized bythat during the shock wave treatment one or more shock waves (9) are generated by means of one or more shock discharges, wherein the shock discharges are preferably generated by one or more high voltage pulses, which are preferably - has / have a frequency in the range of 0.1 Hz to 500 Hz, preferably from 1 Hz to 50 Hz, and / or - have / have a working voltage in the range of 10 kV to 100 kV, preferably from 20 kV to 75 kV, particularly preferably from 30 kV to 50 kV, and / or - has / have a discharge energy in the range from 1J to 12000 J, preferably from 1J to 1000 J, particularly preferably from 1J to 600 J, very particularly preferably 1J to 300 J, in particular 1J to 100 J, for example 1J to 50 J. [3] Method according to one of the preceding claims, characterized by , that - the process medium (2) contains or consists of at least one solvent and optionally at least one additive, wherein the at least one solvent is selected from the group consisting of water, dihydrolevoglucosenone, propylene carbonate, and mixtures thereof, and / or - the at least one binder is selected from the group consisting of sodium carboxymethylcellulose, styrene-butadiene rubber, polyvinylidene fluoride, polyacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, sodium alginate, and mixtures thereof, and / or - the at least one binder dissolves at least partially in the process medium (2), wherein preferably the process medium (2) with the at least one binder dissolved therein is subjected to a separation process for separating the at least one binder from the process medium (2), which separation process is preferably selected from the group consisting of distillation, filtration, and combinations thereof. [4] Method according to one of the preceding claims, characterized by , that - in step c) the disaggregated electrode coating material particles (8) are separated from the process medium (2) by means of at least one separation process selected from the group consisting of centrifugation, sieving, filtration, sedimentation and discharge, as well as combinations thereof, and / or - in step c) the disaggregated electrode coating material particles (8) are first separated from the particle composites and then separated from the process medium (2), wherein the separation of the disaggregated electrode coating material particles (8) from the particle composites is preferably carried out by means of at least one separation method selected from the group consisting of centrifugation, sieving, filtration, sedimentation and discharge, as well as combinations thereof. [5] Method according to one of the preceding claims, characterized by, that - step b) is carried out after step a), step c) is carried out after step b), and after step c) the sequence of steps a) to c) is repeated once or several times, wherein the process medium is circulated and the process medium used in each step a) carried out after a step c) is at least partly the process medium from which the disaggregated electrode coating material particles (8) were separated in the previous step c), or - the process is carried out continuously, wherein the process medium (2) remains in the same container during the process, wherein the particle composites comprising the electrode coating material particles bound with the at least one binder are continuously introduced into the process medium (2) in the container, the disaggregated electrode coating material particles (8) are continuously separated from the particle composites, and the disaggregated electrode coating material particles (8) separated from the particle composites are continuously separated from the process medium (2) in the container, wherein the continuous separation of the disaggregated electrode coating material particles (8) from the particle composites preferably takes place by means of at least one sieve and / or filter,and / or wherein the continuous separation of the disaggregated electrode coating material particles (8) separated from the particle composites from the process medium (2) located in the container preferably takes place via at least one conveyor belt., [6] Method according to one of the preceding claims, characterized by that the disaggregated electrode coating material particles (8) after step c) - are debindered, wherein the debinding is preferably carried out using a process selected from the group consisting of the Soxhlet process, treatment with solvents and / or supercritical fluids, heating, combustion, and combinations thereof, and / or - are sorted, wherein the sorting is preferably carried out using a process selected from the group consisting of sieving, wet sieving, filtering, centrifuging, centrifugal separation, heavy sludge separation, flotation, sedimentation, magnetic separation, eddy current separation, air classification, and combinations thereof. [7] Method according to one of the preceding claims, characterized by that the electrode coating material particles - (battery) active material particles and / or capacitor material particles, and / or - catalyst particles, preferably coated carbon particles and / or - Additive particles, preferably selected from the group consisting of conductive carbon black particles, carbon nanotubes, pore formers, metal particles, and mixtures thereof, and / or - comprise or consist of solid electrolyte particles. [8] Method according to one of the preceding claims, characterized by , that - the particle composites • electrode coatings (10) and / or electrode coating fragments (7) of pure electrodes, or • is black mass, and / or - in step a) no housings and / or housing fragments of energy storage devices and / or energy converters are introduced into the process medium (2). [9] Method according to one of the preceding claims, characterized by that the particle composites - to • electrode coatings (10) separated from electrode substrates (11), and / or • electrode coating fragments (7) separated from electrode substrates (11) and / or electrode substrate fragments, or - solidified electrode coating pastes, or - to • electrode coatings (10) arranged on electrode substrates (11), and / or • electrode coating fragments (7) arranged on electrode substrates (11) and / or electrode substrate fragments are of single-variety electrodes and / or of electrodes each comprising at least one binder that is at least partially soluble in the process medium (2), or - are mixtures of these. [10] Method according to one of the preceding claims, characterized by that in step a) only - Particle composites which were obtained or are obtained before step a) by coating coated electrode substrates and / or fragments of coated electrode substrates, preferably by grinding and / or pressure wave treatment, being / being decoated, whereby a mixture of electrode substrate fragments and the particle composites was / are obtained, and the particle composites were / are separated from the electrode substrate fragments, preferably by sieving, and were / are optionally crushed, whereby the coated electrode substrates and / or fragments of coated electrode substrates are or were obtained preferably by dismantling energy storage devices and / or energy converters and / or by crushing energy storage devices and / or energy converters and subsequently separating the fragments obtained by crushing, and / or - Particle composites which were obtained or are obtained before step a) by dismantling energy storage devices and / or energy converters, whereby electrodes were / are obtained, and the electrodes were / are subjected to a sorting process in which pure electrodes comprising the particle composites and / or electrodes which each comprise at least one binder which is at least partially soluble in the process medium (2) were / are obtained by separating them from all remaining electrodes, wherein the electrodes obtained were / are optionally crushed, and / or - Particle composites that have arisen as rejects in the form of electrode coatings and / or electrode coating fragments during the manufacture of electrodes, energy storage devices and / or energy converters, and / or - Particle composites which have accrued as rejects in the form of electrodes during the manufacture of electrodes, energy storage devices and / or energy converters and which have subsequently been / are subjected to a sorting process in which pure electrodes comprising the particle composites and / or electrodes which each comprise at least one binder which is at least partially soluble in the process medium (2) have been / are obtained by separating them from all remaining electrodes, wherein the resulting electrodes have optionally been / are crushed, and / or - particle composites that have arisen as rejects and / or residues in the form of solidified electrode coating pastes during the production of electrode coating pastes, and / or - Black mass, introduced into the process medium (2). [11] Method according to one of the preceding claims, characterized by that the particle composites are at least partly - electrode coatings (10) arranged on electrode substrates (11), and / or - electrode coating fragments (7) arranged on electrode substrates (11) and / or electrode substrate fragments, wherein the at least one shock wave treatment at least partially removes the coating from the electrode substrates (11) and / or electrode substrate fragments and thereby obtains de-coated electrode substrates (11) and / or de-coated electrode substrate fragments, and wherein the at least one shock wave treatment at least partially disaggregates the particle composites and thereby obtains disaggregated electrode coating material particles, and wherein preferably - the stripped electrode substrates (11) and / or stripped electrode substrate fragments are separated from the process medium, preferably by means of a separation process selected from the group consisting of centrifugation, sieving, filtration, sedimentation and discharge, as well as combinations thereof, and / or - the disaggregated electrode coating material particles (8) are separated from the process medium (2), preferably by means of a separation process selected from the group consisting of centrifugation, sieving, filtration, sedimentation and discharge, as well as combinations thereof, and / or - the stripped electrode substrates (11) and / or stripped electrode substrate fragments are separated from the disaggregated electrode coating material particles (8), preferably by means of a separation process selected from the group consisting of sieving, washing, and combinations thereof. [12] Device for the disaggregation of particle composites, comprising a reactor (1) with a device for generating shock waves, a container for a process medium (2), in which the reactor (1) is at least partially arranged, at least one filling device (3) for filling the reactor (1) with particle composites comprising or consisting of electrode coating material particles bound with at least one binder, and at least one first separation device (4) for separating disaggregated electrode coating material particles (8) from the process medium (2). [13] Device according to claim 12, characterized by , that - the device for generating shock waves is suitable for generating shock waves by means of one or more shock discharges, wherein the shock discharges are preferably generated by one or more high-voltage pulses, which are preferably • has / have a frequency in the range of 0.1 Hz to 500 Hz, preferably from 1 Hz to 50 Hz, and / or • have / have a working voltage in the range of 10 kV to 100 kV, preferably from 20 kV to 75 kV, particularly preferably from 30 kV to 50 kV, and / or • has / have a discharge energy in the range from 1 J to 12000 J, preferably from 1 J to 1000 J, particularly preferably from 1 J to 600 J, very particularly preferably 1 J to 300 J, in particular 1 J to 100 J, for example 1 J to 50 J, and / or - the at least one filling device (3) is at least one filling device for filling, preferably continuously filling, the reactor with particle composites comprising or consisting of electrode coating material particles bound with at least one binder, wherein the at least one filling device (3) is preferably at least one conveyor belt, and / or - the at least one first separation device (4) is at least one separation device for separating, preferably continuously separating, disaggregated electrode coating material particles (8) separated from the particle composites from the process medium (2), wherein the at least one first separation device (4) is preferably at least one conveyor belt, at least one sieve, and / or at least one filter, particularly preferably at least one conveyor belt. [14] Device according to claim 12 or 13, characterized by that the device additionally - at least one second separation device (5) for separating, preferably continuously separating, the disaggregated electrode coating material particles (8) from the particle composites, wherein the at least one second separation device (5) is preferably at least one sieve and / or at least one filter, wherein the at least one sieve and / or the at least one filter particularly preferably has a mesh size of at most 50 µm, and / or at least one third separation device for separating stripped electrode substrates (11) and / or stripped electrode substrate fragments from the process medium (2), wherein the at least one third separation device is preferably at least one conveyor belt, at least one sieve, and / or at least one filter, particularly preferably at least one sieve, or - at least one combined separation device (6) for separating, preferably continuously separating, the disaggregated electrode coating material particles (8) from the particle composites and for separating, preferably continuously separating, stripped electrode substrates (11) and / or stripped electrode substrate fragments from the process medium (2), wherein the at least one combined separation device (6) is preferably at least one conveyor belt with at least one integrated sieve, wherein the at least one integrated sieve particularly preferably has a hole or mesh width of at most 5 mm, preferably at most 1 mm, particularly preferably at most 50 µm. [15] Method according to one of claims 1 to 11, characterized by that it is carried out with a device according to one of claims 12 to 14.

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