Recycling process for components of electrochemical energy storage devices and recycling facility therefor

Abstract

Recycling process for components of electrochemical energy storage devices, namely batteries with electrodes having electrode carrier foils and an electrode coating applied thereto, comprising the steps a) comminution (16) of battery material, such as production waste arising from the production of batteries, active and deactivated batteries or battery cells, into battery comminution material comprising particles of the electrode carrier foils and particles of the electrode coatings, b) mechanical deagglomeration (18) of the particles of the electrode coatings contained in the battery crushing material, characterized in that c) the step of mechanical deagglomeration (18) is carried out for such a long time and / or intensively until the maximum size of the particles of the electrode coatings no longer exceeds 100 µm on average by mass, and d) the electrode coatings are comminuted to a particle size distribution such that the average diameter of the particles of the electrode coatings after mechanical deagglomeration is at most 1 / 10 of the average size of the particles of the electrode carrier foils, based on the maximum Feret diameter of the particles of the electrode carrier foils.

Description

[0001] The invention relates to a recycling process for components of electrochemical energy storage devices, namely batteries, according to the preamble of claim 1 and to a recycling device according to the preamble of claim 22 for carrying out such a recycling process.

[0002] The invention relates to the recycling of batteries that have electrodes formed with electrode carrier foils and an electrode coating applied thereto. These include, in particular, lithium-ion batteries.

[0003] Recycling processes for lithium-ion batteries are described in numerous prior art documents. Examples include WO 2018 / 218 358 A1, DE 10 2011 110 083 A1, and WO 2022 / 032 345 A1.

[0004] The production of lithium-ion batteries is of enormous importance for mobile and stationary energy storage and thus for the widespread use of renewable energies with a favorable CO2 footprint. However, the CO2 footprint of the battery's life cycle depends to a comparatively large extent on the CO2 footprint of the raw materials it contains. Through efficient recycling of raw materials in energy-efficient processes, the CO2 footprint of mobile and stationary energy storage in lithium-ion batteries can be very positively influenced. The primary goal of this invention is to achieve significant savings in CO2 emissions through a more efficient recycling process for lithium-ion batteries and production waste materials from lithium-ion batteries.

[0005] Damaged or aged primary and secondary (rechargeable) lithium-ion batteries and lithium-metal batteries (hereinafter collectively referred to as lithium batteries) are also hazardous and therefore difficult to transport, especially if damaged. High transport and storage costs arise.

[0006] Lithium batteries pose the following dangers: - Electrical hazards due to high voltage, which also provides activation energy for further exothermic reactions, - Chemical hazards from exothermic organic substances and from thermally decomposable, fluorine-containing components, which can result in the release of hydrogen fluoride and other fluorine components, and - Risk of fire and explosion, as internal and external short circuits can lead to local heating, so that pressure can build up and ultimately lead to explosion.

[0007] Due to these hazards, the storage, transport and recycling of these components is expensive and technically challenging.

[0008] When processing lithium batteries, further safety issues must also be considered: - Lithium-ion batteries pose an electrical hazard, for example through reaction activation by electrically stored energy in such batteries; in particular, internal and external short circuits in aged, damaged or faultily manufactured batteries can cause dangerous fires with hazardous exhaust gases that spread rapidly via chain reactions. - Solvents from electrolytes contained in such batteries are flammable. - An exothermic decomposition of fluorine-containing components (e.g. conductive salt LiPF6 (lithium hexafluorophosphate) and binder PVDF (polyvinylidene fluoride)) of such batteries can lead to the formation of dangerous hydrogen fluoride in the event of fire (also in contact with atmospheric moisture during the recycling process or in the case of damaged batteries). - Cathodic active materials of such batteries sometimes contain nickel and cobalt oxides and are carcinogenic. - There is a risk of dust explosion due to the formation of dust during the processing of such batteries.

[0009] A further problem is that lithium batteries from power tools, e-bikes, electric vehicles, and industrial batteries, which are returned by consumers or accrue as production waste, are generated in a decentralized manner. In particular, the unwanted production of scrap lithium batteries occurs in a decentralized manner in the respective factories. Such scrap is particularly difficult to store, transport, and recycle because the scrap states are not defined. The safety status of the batteries and the necessary protective measures for safe storage and transport can therefore neither be planned in advance nor classified later. This creates a high safety risk, which not only poses high risks to health and the environment, but also high financial risks.

[0010] Lithium batteries contain valuable components such as cobalt, nickel, lithium, copper, and aluminum. If the batteries are processed in a recycling facility, the transition metals (cobalt, nickel, manganese), lithium, copper, and aluminum can be recycled.

[0011] Particularly valuable raw materials from lithium batteries and the waste from lithium battery production are bound in the coatings of the electrodes. Conventional recycling processes do not selectively shred the batteries (and the production waste) in the initial steps, although – as recognized by the present invention – selective decoating would lead to greater selectivity and thus to higher recycling efficiency (the higher recovery rate of the valuable materials cobalt, nickel, manganese, and copper) as well as to improved energy efficiency of the recycling process.

[0012] The present invention aims to achieve a decentralized transfer of no longer required or defective lithium batteries into a transportable state in functional integration with the implementation of a selective deagglomeration of the electrode coatings.

[0013] The present invention has recognized that selective deagglomeration is advantageous for the following reasons: In battery recycling, valuable raw materials, such as in particular cobalt, nickel, lithium, graphite, copper, aluminum, manganese, iron, plastics and organic carbonates of the electrolyte, should be kept in the material cycle as efficiently as possible with the lowest possible energy consumption.

[0014] However, since metals, plastics, other organic components and graphite generally require different recycling processes, a clean separation of the materials is necessary before the production of industrially usable intermediate products.

[0015] The present invention further recognizes that the fractions of the various materials (material fractions) should be concentrated as much as possible without losing or devaluing substantial amounts of material. In particular, the recovery of lithium and graphite is often sacrificed in the prior art for the simple recovery of cobalt and nickel. Graphite is oxidized by thermal treatment, burned, or disposed of as a filter cake. Lithium is often lost in the slag of pyrometallurgical processes or in the flue dust from smelting processes.

[0016] Deagglomeration separates the various material particles of graphite, lithium metal oxides (or other cathodic battery active materials), and aluminum and copper foils (both current collector foils) bound by a binder, resulting in the smallest possible individual particles of the graphite and cathodic active material coating materials. Only when the coating materials are as small as possible, as far removed from the coating layer as possible, and as isolated as possible can they be separated particularly effectively from each other and from the current collector foils based on their physical properties, such as density (special case: buoyancy), particle size, flow behavior, or surface properties.

[0017] In the state of the art, existing bonds between the current collector (aluminum and copper foils) and the coating material (Li, Ni, Co-containing oxides and graphite) are broken either by burning the binder in thermal processes or by mechanical comminution processes.

[0018] When the binder is burned, it decomposes along with the electrolyte and parts of the graphite. These components can then no longer be recovered, and recycling efficiency is reduced. In addition, toxic and chemically aggressive fluorine compounds are formed, which require complex scrubbing from the exhaust gas.

[0019] In conventional mechanical processes, such as two- to three-stage shredding, all materials are shredded together to a similar final particle size. This process does not involve multiple processing of each piece of film, so 10-30% of the valuable coating materials remain attached to the current collector films and are thus removed from the film fraction of the recycling process.

[0020] In addition, in conventional processes the current collector foils (Cu, Al) are also crushed, resulting in impurities of Cu and Al that cannot be screened out in the finer fractions of the separated coating materials.

[0021] Traditionally, battery recycling is only possible at a few locations with limited recycling efficiency and higher energy consumption. Damaged and aged batteries must be transported to these locations and stored there until they can be processed.

[0022] To reach the recycling site, defective batteries must traditionally be transported for recycling in special containers filled with a filling medium. Transport often requires special permits. Furthermore, transport containers are often only approved for a specific battery system, increasing weight- and volume-based transport costs.

[0023] Batteries are stored before recycling. Spontaneous combustion and subsequent major fires also frequently occur in these storage areas.

[0024] Even after conventional shredding of non-deactivated batteries in ambient air or under nitrogen, galvanic elements remain – due to residual functional coatings on the current collectors – which can lead to local short circuits and cause further exothermic reactions. This triggers chain reactions and can lead to fires during or after shredding and in storage.

[0025] Traditionally, batteries or battery cells are largely recycled using pyrometallurgical processes (particularly through melting and slag separation) or a combination of thermal processing steps and hydrometallurgy. These processes are energy-intensive and, at the current state of technology, unsuitable for the recovery of lithium and aluminum. Furthermore, they generate emissions in the form of fluorine-containing exhaust gases.

[0026] Another known solution from EP 3 289 627 B1 is a method for treating used lithium batteries with the steps: (a) crushing the batteries to obtain shredded material, (b) inactivating the comminuted material by drying to obtain an inactivated comminuted material, wherein (c) drying is carried out at a pressure not exceeding 300 hPa and a temperature not exceeding 80 °C, and (d) the inactivated shredded material is placed in a transport container.

[0027] Paragraph

[0009] of patent EP 3 289 627 B1 describes that inactivation is carried out by drying the material to be comminuted in such a way that so much electrolyte can be removed that an electrochemical reaction is no longer possible or only possible to a negligibly small extent.

[0028] The disadvantage of this solution is that even under an inert atmosphere during the shredding / processing of still active, charged batteries in the shredding chamber, the highly exothermic fire reactions described above can occur, forming toxic fluorine-containing gases.

[0029] Another disadvantage of this solution according to EP 3 289 627 B1 is that the resulting shredded material can be exposed to an oxygen- and / or moisture-containing ambient atmosphere immediately after drying. During storage and transport of the materials, toxic and corrosive byproducts can form in the transport container described in EP 3 289 627 B1.

[0030] The recycling process known from EP 3 312 922 B1 for treating used, particularly rechargeable, batteries does not disclose a transport container. However, the material must be temporarily stored in intermediate containers, so these reactions can occur in the intermediate containers.

[0031] The combination of these disadvantages—i.e., the processing of non-discharged batteries with their filling into transport containers with potentially humid, oxygen-rich atmospheres—is potentially dangerous. This is due to the fact that in shredded products from lithium batteries that have not been deactivated through complete deep discharge, the reactive metal lithium (in its metallic form) is present on the graphitic anode. This metal reacts strongly exothermically with oxygen or water (from atmospheric moisture), and these reactions can lead to spontaneous combustion of the transport containers.

[0032] A further disadvantage of the process according to EP 3 312 922 B1 is that the energy required to deform metals during mechanical comminution is partially dissipated as heat. This leads to heating of the comminution material during comminution processes. Battery modules are encased in metal sheets and contain metal components. The battery cell housings are also largely made of formed metal sheets.

[0033] In particular, the rapid comminution of large quantities of batteries, which is desirable for economic reasons, results in warm comminution material. This comminution material, with its stored heat, provides the activation energy for the decomposition reactions of the electrolyte salt described above, as well as any organic carbonates remaining in the comminution material in the presence of humidity or atmospheric oxygen.

[0034] A further disadvantage of the above-described processes involving material handling and transport containers is that carcinogenic products (e.g., cathode powders with hazard warnings in categories 350, 350i, and 351) must be filled and transported. These filling, packaging, and transfer processes contain the potential for the release of dust and carbon nanotubes (CNTs).

[0035] A further disadvantage of the state of the art according to EP 3 289 627 B1 and DE 10 2012 024 876 A1 is that the cohesive bulk material and shredded material compacts during transport and storage and subsequently forms bulk material bridges, so that a defined, low-dust emptying without human intervention is difficult.

[0036] A further disadvantage is that the throughput of the plant with permanently installed mixers in the modular concept shown in decentralized containers is determined by the drying speed.

[0037] In order to increase the plant throughput, the economically minded user will choose the minimum drying criterion of reduced fire hazard (see e.g. EP 3 289 627 B1 and DE 10 2012 024 876 A1) as the process criterion for determining the minimum drying time and maximizing the plant throughput.

[0038] Many types of lithium batteries contain cobalt and nickel oxides or their compounds, which are classified as carcinogenic. Aged or damaged lithium battery cells, battery modules, and battery systems must therefore be recycled. This recycling must involve a high proportion of material recovery to significantly improve the carbon footprint of battery production.

[0039] Recycling lithium batteries is not trivial, as they pose chemical, electrical, and fire hazards. The transport of aged and damaged batteries is particularly complex and dangerous. Fires in transport vehicles, warehouses, and recycling facilities are a frequent occurrence due to spontaneous combustion and poor process management. The goal of lithium battery recycling is to separate all valuable components so that they can be processed efficiently and properly.

[0040] The present invention has recognized that it is advantageous that all the lithium stored in the (partially) charged state in the anode can be safely converted into the metal oxide compound of the cathode, so that a) no residues of metallic lithium reactive with water and atmospheric moisture are present in the deactivated material, b) metallic lithium can no longer react with the organic carbonates of the battery electrolyte, because this would mean: i) Binding of lithium in carbonate compounds, which are more difficult to recover in standardised metallurgical processes, ii) Reaction of the organic carbonates DMC (dimethyl carbonate), EMC (ethyl methyl carbonate), EC (ethylene carbonate), which cannot then be recovered as components of the battery electrolyte, and iii) formation of flammable gases, e.g. methene, methane or propane, as by-products, c) the lithium can be extracted in a targeted and concentrated manner from the metal oxides of the cathodic active material during the subsequent metallurgical processing steps, while the anodic graphite can be separated in advance, d) the lithium does not contaminate the graphite fraction, and the graphite can therefore be recovered cleanly and efficiently.

[0041] The present invention has further recognized that it is advantageous if the inactivation of the batteries can be achieved without the formation of fluorine-containing exhaust gases and without the risk of fire.

[0042] The present invention has further recognized that it is advantageous to increase the packing density of the battery materials to be transported.

[0043] The present invention has further recognized that it is advantageous to provide dust-free, solvent-free storage, filling and emptying of the battery fragments into transport containers.

[0044] The present invention has further recognized that it is advantageous to provide a simple filling and emptying of the storage containers (with extremely cohesive bulk material).

[0045] The present invention has further recognized that it is advantageous to enable outdoor storage by preventing the penetration of moisture into the battery fragments.

[0046] The present invention has further recognized that it is advantageous to enable high recycling efficiency by preparatory good separation of current collector foil (Al, Cu) and coating materials (Co, Ni, Mn, Li mixed oxides and graphite) and the selective deagglomeration of the coating materials without thermal decomposition of the binder.

[0047] The present invention has further recognized that it is advantageous to achieve high energy efficiency of the recycling process.

[0048] The present invention has further recognized that it is advantageous to enable inert transport using inert gas, nitrogen or vacuum.

[0049] The present invention further recognized that if the organic carbonates are not removed by vacuum drying at moderate temperatures, they react with the conductive salt LiPF6 present in the battery to form, among other substances, fluorophosphates (dimethyl fluorophosphate (DMFP) and diethyl fluorophosphate (DEFP)). These substances are so harmful that they can be used as chemical weapons.

[0050] The present invention has further recognized that it is advantageous if the organic reagents are removed so that they cannot react further during storage and transport.

[0051] The present invention has further recognized that the hazard of crushed lithium battery fragments is reduced by electrolyte removal, since flammable components have been removed and thus a flammable atmosphere can no longer form in the containers to be transported.

[0052] The invention is therefore based on the object of avoiding the above-mentioned disadvantages of conventional battery recycling.

[0053] The invention solves this problem with the features of a recycling method according to claim 1 and with a recycling device having the features according to claim 22.

[0054] The recycling process according to the invention for components of electrochemical energy storage devices, namely batteries with electrodes comprising electrode carrier foils and electrode coatings applied thereto, accordingly provides for the following steps: a) Comminution of battery material, such as production waste arising from the production of batteries, active and deactivated batteries or battery cells, into battery comminution material comprising particles of the electrode carrier foils and particles of the electrode coatings, b) mechanical deagglomeration of the particles of the electrode coatings contained in the battery crushing material, preferably at temperatures below the decomposition temperature of a binder contained in the electrodes, c) the mechanical deagglomeration step is carried out for such a long time and / or intensively until the maximum particle size of the electrode coatings no longer exceeds 100 µm by mass, and d) the electrode coatings are comminuted to a particle size distribution such that the average diameter of the particles of the electrode coatings after mechanical deagglomeration is at most 1 / 10 of the average size of the particles of the electrode carrier foils, based on the maximum Feret diameter of the particles of the electrode carrier foils.

[0055] The invention preferably utilizes an intensive interaction between particles by mixing in order to achieve a small particle size of the particles of the electrode coatings, while the size of the particles of the electrode carrier foils is significantly larger.

[0056] Preferably, deagglomeration occurs through the introduction of mechanical energy.

[0057] Preferably, the particle size distribution of the cathodic electrode coatings after deagglomeration has a median value x 50 which is less than four times the median value x 50the particle size distribution of cathodic active materials contained in the cathodic electrode coatings, which are contained in the electrode to be recycled. The particle size is measured or determined by analysis of the commercially available active material or by electron micrographs of the electrode structure. Measurement of the particle size during implementation of the method according to the invention is not necessary, but can be provided in a preferred embodiment of the invention. The aforementioned particle size distribution is preferably obtained by deagglomeration for as long and / or as intensively until it is established. The duration and / or intensity of the deagglomeration are determined in advance, e.g.experimentally, and values ​​for the duration and / or intensity of deagglomeration, depending on the material quantities and material compositions, are stored in one or more tables, which are used when implementing the method to determine the required duration and / or intensity of deagglomeration. Alternatively, the median value x is 50 the particle size distribution of the cathodic electrode coatings after deagglomeration is less than 10 to 20 times the median value x 50 the particle size distribution of cathodic active material contained in the cathodic electrode coatings in the electrode of lithium iron phosphate batteries to be recycled.

[0058] The particle size of the cathodic active material is in turn measured or determined by analysis of the commercially available active material or by electron micrographs of the electrode structure, whereby a measurement of the particle size during the implementation of the method according to the invention is not necessary, but can be provided in a preferred embodiment of the invention. The aforementioned particle size distribution is preferably obtained by deagglomerating for as long and / or as intensively as necessary until it is established. In this case, the duration and / or intensity of the deagglomeration are in turn determined in advance, e.g. experimentally, and values ​​for the duration and / or intensity of the deagglomeration are stored in one or more tables as a function of material quantities and material compositions. These tables are used when implementing the method to determine the required duration and / or intensity of the deagglomeration.

[0059] The focus is on the deagglomerated individual particles or the particle size distribution of the active material before coating.

[0060] The invention preferably provides that the binder is not thermally decomposed prior to deagglomeration. This means that mechanical deagglomeration is preferably carried out at temperatures below the decomposition temperature of the binder.

[0061] Preferably, the processing of non-deactivated battery material is carried out at temperatures above 80 °C, which has proven advantageous in combination with mechanical deagglomeration.

[0062] Preferably, the battery shredded material is not dried before deagglomeration.

[0063] The invention preferably further provides that the battery shredded material contains components of the materials of the casings of battery cells.

[0064] Preferably, the invention provides that the deagglomeration is controlled or determined based on the porosity and / or pore radius distribution of the particles of the electrode coatings and / or the particles of the electrode carrier foils.

[0065] Preferably, the mechanical deagglomeration is carried out with a specific power input by means of a deagglomeration device for a period of at least one minute, preferably at least 2 minutes, particularly preferably at least 5 minutes, with at least 50 watts per kilogram, preferably 70 watts per kilogram, particularly preferably 100 watts per kilogram, of battery active materials contained in the comminution material.

[0066] According to a further development of the invention, a further step following the deagglomeration of separating the particles of the electrode coatings from the dried comminution material by screening and / or sieving is provided.

[0067] A further development of the invention provides for drying or recovery of solvent contained in the electrolyte of the battery, preferably organic solvent, in a machine.

[0068] According to a further development of the invention, the drying is used to also dry out coolants or extinguishing agents, for example water, from a wet comminution preceding the drying.

[0069] A further development of the invention provides that the comminution and drying steps are combined and carried out in an explosion-proof manner in a drying chamber of the machine in which negative pressure or vacuum prevails. Explosion protection is achieved by monitoring the pressure in this drying chamber. The pressure resistance of the machine is preferably determined such that, in the event of an explosion, the pressure increase in the machine results in maximum forces acting on the machine that can be tolerated by the machine. The operating pressure in this drying chamber is preferably in the range of one-twentieth to one-fifth of the pressure resistance of the machine.

[0070] According to a further development of the invention, the duration of drying during operation is determined and controlled as a function of a combination of measured values ​​of the proportion of volatile organic carbons in the drying gas as well as the absolute pressure and / or the rate of change of the absolute pressure in the drying chamber.

[0071] A further development of the invention provides that the galvanic elements of the batteries are deactivated by deep electrical discharge before comminution, so that an electrochemical reaction is no longer possible.

[0072] According to a further development of the invention, it is provided that the materials to be recycled are components of batteries that were once electrically charged and then deactivated, the deactivation being carried out by a) Deep discharge and / or b) removing the electrolyte by vacuum drying, preferably at a pressure of 0 to 600 mbar, preferably at temperatures <80 °C and / or c) thermal removal of the electrolyte at temperatures >80 °C and / or d) crushing in aqueous solution and / or e) Crushing into coolant / extinguishing agent and / or f) Crushing / mixing with a binding agent, e.g. lime, lime milk.

[0073] The removal of the electrolyte can be carried out either by vacuum drying at a pressure of 0 to 600 mbar or by thermal removal of the electrolyte at temperatures >80°C or first by vacuum drying at a pressure of 0 to 600 mbar and subsequent thermal removal of remaining electrolyte at temperatures >80°C.

[0074] A further development of the invention provides that the materials to be recycled are production waste from the electrode production for lithium batteries or from the lithium battery production, preferably from lithium batteries that have never been electrically charged.

[0075] Advantageously, deactivation of batteries that have never been electrically charged does not have to occur, since the battery materials are already electrochemically inactive.

[0076] According to a further development of the invention, the batteries to be recycled comprise composite materials of electrode assemblies including electrode carrier foils with electrode coatings and separator foils applied thereto.

[0077] A further development of the invention provides that after comminution, the battery shredded material is stored and transported in a gas-tight and dust-tight transport mixer, wherein the transport mixer comprises: a) a mixing tool for mechanically mixing and loosening the battery shredded material, b) a connection option for an active discharge aid or a permanently installed active discharge aid or a conveyor unit for discharging the battery shredded material and c) Means for inerting and / or evacuating the transport mixer and for repeatedly adding gas to the transport mixer, venting gas from the transport mixer and / or creating a vacuum in the transport mixer when the transport mixer is filled with battery shredded material without generating dust.

[0078] The transport mixer is characterized by the fact that it can be transported in its full state without additional packaging, preferably by crane, forklift, by road, at sea, and / or by rail. For example, the transport mixer comprises a sea freight container, also known as an ISO container, e.g., in the form of a 20-foot ISO container or a 40-foot ISO container, as defined, for example, in ISO standard 668. It preferably includes container corners (e.g., according to ISO standard 1161) and / or forklift lugs to enable handling by forklift. The container contains devices for mixing the battery shredded material, a dust-tight, in particular airtight, closable filling opening for filling the battery shredded material and a conveyor unit for discharging the battery shredded material through a discharge opening that is also dust-tight, in particular airtight, closable and, if necessary,Devices for inerting and / or evacuating the interior of the container and / or devices for heating the interior are provided.

[0079] The use of such a special container is advantageous because it ensures the transport and storage of large quantities of battery shredded material cost-effectively and as safely as possible. The large volume of such a container provides ample space for transporting, storing, and mixing the battery shredded material. The multifunctionality of such a transport mixer can keep the number of transfer processes to a minimum. This is advantageous because it prevents any dust escaping during transfer from the container to the environment. Since battery shredded material often contains carcinogenic materials, their distribution into the environment via dust is detrimental and can be prevented by using such a transport mixer.

[0080] According to a further development of the invention, the battery shredded material is dried for a long time in the transport mixer, for example over a period of more than 30 minutes, whereby a) long-term drying before deagglomeration or b) deagglomeration before long-term drying or c) deagglomeration and long-term drying are carried out simultaneously. Deagglomeration preferably takes place through intensive mixing.

[0081] A further development of the invention provides that drying heat is introduced into the transport mixer, for example by introducing a tempering liquid into a double jacket surrounding the drying chamber for tempering the walls of the drying chamber and / or by heating a heating jacket surrounding the drying chamber.

[0082] According to a further development of the invention, the drying heat is supplied over a longer period of time, for example, more than 30 minutes, and at a low temperature level, for example, at a temperature below 100°C, preferably below 80°C, and particularly preferably below 60°C. Preferably, the drying heat is supplied by using a heat pump and / or using waste heat from units and processes other than those used in the recycling process.

[0083] Such low temperatures lead to fewer undesirable side reactions caused by the decomposition of conductive salt and organic carbonates and additives. For example, the formation of hydrogen fluoride in the gas atmosphere of the transport mixer during post-drying can be kept below 100 ppm, preferably below 30 ppm, in the exhaust stream.

[0084] Such low temperatures lead to higher energy efficiency, since heat pumps operate with a higher coefficient of performance at smaller temperature differences and the supply of the evaporation enthalpy of the electrolyte solvents required for evaporation can be carried out particularly energy-efficiently.

[0085] A further development of the invention provides that after the steps of comminution and intensive mixing, the transport mixer is used for subsequent drying.

[0086] According to a further development of the invention, the transport mixer is connected to a drying system.

[0087] A further development of the invention provides that the transport mixer is connected via a feed system for supplying the battery material or via a gas pipe connection to a drying and condensation circuit of a preparation plant for comminuting the battery material and for electrolyte recovery.

[0088] According to a further development of the invention, it is provided that the transport mixer is protected against an explosion by means of an explosion protection device, wherein the explosion protection device a) a device for monitoring the pressure in the drying room, b) a device for monitoring volatile organic carbon in the drying gas, and / or c) has a device for monitoring oxygen in the drying gas and / or drying chamber.

[0089] A further development of the invention provides that in the transport mixer the battery shredded material is transported on roads, rails and / or ships to a processing location and is connected there to a processing plant, in particular a drying system of the processing plant, and / or is emptied into this processing plant.

[0090] The object underlying the invention is further achieved by a recycling device which is designed for recycling components of electrochemical energy storage devices, namely batteries with electrodes which have electrode carrier foils and an electrode coating applied thereto, the recycling device comprising: a) a comminution unit for comminuting deactivated or non-electrochemically active battery material, such as production waste arising from the production of batteries, deactivated batteries or battery cells, into battery comminution material comprising particles of the electrode carrier foils and particles of the electrode coatings, b) a deagglomeration device for the mechanical deagglomeration of the particles of the electrode coatings contained in the battery crushing material, preferably an intensive mixer for the intensive mixing of these particles, preferably at temperatures below the decomposition temperature of a binder contained in the electrodes, c) wherein the deagglomeration device has a control device which is designed to carry out the mechanical deagglomeration for such a long time and / or intensively until the maximum size of the particles of the electrode coatings no longer exceeds 100 µm on average by mass and the electrode coatings are comminuted to a particle size distribution such that the average diameter of the particles of the electrode coatings after the mechanical deagglomeration is at most 1 / 10 of the average size of the particles of the electrode carrier foils, based on the maximum Feret diameter of the particles of the electrode carrier foils.

[0091] According to further developments of the invention, this recycling device has means for carrying out the method steps according to the invention.

[0092] Further developments of the invention will become apparent from the claims, the description, and the drawings. The aforementioned features and their advantages, as well as combinations of several features, are exemplary and can be used alternatively or cumulatively without the advantages necessarily having to be achieved by embodiments according to the invention. Further features can be seen from the drawings. The combination of features of different embodiments of the invention or features of different claims is also possible, deviating from the selected references to the claims, and is hereby proposed. This also applies to features that are shown in separate drawings or mentioned in their description. These features can also be combined with features of different claims. Likewise, features listed in claims can be omitted for further embodiments of the invention.

[0093] The drawing shows: Fig. 1 shows a schematic representation of an embodiment of a recycling process according to the invention.

[0094] Fig.1 shows an embodiment of a recycling process 10 according to the invention, which is carried out in a modular recycling facility for carrying out the process steps according to the invention. The steps of deactivating the batteries through discharge, electrolyte recovery, material preparation through separation of the materials, and further metallurgical processing of the valuable metals are decoupled from one another, so that different process routes can be combined depending on the regional material supply and quantities, the condition of the batteries or battery production waste, and the downstream processes. For example, decentralized discharge can take place first, followed by electrolyte recovery, and then products from the battery recycling process can be fed into a pyro- or hydro-route.

[0095] The modules of the modular system are based on the desired capacity and combine the process steps described below. 1. Deactivating the batteries - Step 12:

[0096] If the battery components or the battery itself are electrochemically charged, they are first electrochemically deactivated. If the battery elements are not yet electrochemically activated or have otherwise become electrochemically inactive, deactivation is not necessary.

[0097] The production waste of lithium batteries is not yet electrochemically active before the forming and initial charging process. A battery can self-deactivate through self-discharge to zero volts. a) Deactivating the batteries by deep discharging: Preferably, the batteries are deactivated before shredding by deep discharging them and then short-circuiting them. The short circuit lasts for a period of time determined such that no relaxation behavior occurs after this time, e.g., more than 6 hours, more than 12 hours, or preferably more than 24 hours.

[0098] The batteries are discharged to extract their stored electrical energy, which could otherwise trigger further exothermic reactions. Discharge occurs, for example, via an electrical load (resistor, consumer) or by feeding back into the power grid. Discharge can also occur via an ion-conducting liquid, which is particularly useful when the batteries can no longer be discharged by other means.

[0099] The discharge is preferably temperature-controlled. For example, if the measured outside temperature exceeds 60°C, the discharge is interrupted, and at temperatures above 100°C, a cooling process is initiated. In one embodiment, the cooling process can be carried out by immersion in a preferably cooled basin filled with deionized water. Deionized water is non-conductive, so cell / contact electrolysis is not possible. Preferably, an ion exchanger and a cooling device are connected in circulation to a basin provided for the cooling process, so that ions introduced by contamination and batteries are removed from the water.

[0100] In the event of spontaneous combustion of the battery, there is sufficient extinguishing water available to prevent the formation of flash flames and to extinguish the battery by cooling it down.

[0101] With such external cooling, discharge can be up to 10 times faster because the resulting heat is continuously dissipated.

[0102] Preferably, the short circuit is closed after zero volts has been reached between the battery electrodes under deionized water, and the battery is left short-circuited in a cooling tank / relaxation tank until no more heat is generated in this tank. In one embodiment, the battery tanks are connected in series to serve multiple tanks with an ion exchanger, activated carbon, and a cooling unit. Preferably, the water inlet and outlet temperatures are then compared. When both temperatures are equal, the reaction is complete. This allows the energy dissipated per battery to be balanced during the discharge process, and the discharge rate to be specifically maximized.

[0103] Another possibility is to place a thermocouple on the battery and a thermocouple in the water. If there is no temperature gradient, the reaction is complete.

[0104] The lithium in a secondary lithium-ion battery is largely re-incorporated into the metal lattices of the transition metal oxides and is therefore no longer present in its reactive metallic form on the graphite electrode.

[0105] After this step, only deactivated galvanic elements remain. There is no electrochemical potential difference between the electrodes. Chemical equilibrium is reached. Electrochemical reactions are not possible in this state. b) Deactivation of the batteries by removing the electrolyte by vacuum drying at pressures preferably between 0 and 600 mbar and preferably at temperatures below 80 °C. c) Deactivation of the batteries by thermal pretreatment: Alternatively, electrochemical deactivation occurs by heating the battery or the shredded battery to temperatures above 80 °C and drying out the electrolyte. d) Deactivating the batteries by freezing the electrolyte: Alternatively, temporary electrochemical deactivation occurs by freezing the battery's electrolyte to temperatures below its freezing point. 2. Disassembly - Step 14:

[0106] To dismantle the deactivated batteries to module or stack size, a dismantling module is provided with tools, personal protective equipment, and suitable lifting tables. For smaller capacities, discharging and dismantling are preferably housed in a single module.

[0107] This module, in particular, is preferably designed independently of the other modules with the highest mobility characteristics. Highly mobile designs include, for example, ISO containers, truck trailers, semi-trailers, and a fixed truck body. 3. Shredding - Step 16:

[0108] Deactivated battery systems, battery modules, or battery cells are fed into a comminution unit A via an inert gas-purged or evacuatable lock 15. The comminution unit A is preferably designed to be pressure-shock resistant, gas-tight, and vacuum-tight.

[0109] Furthermore, crushing is carried out under an inert gas atmosphere, in a vacuum or in an atmosphere supersaturated with volatile organic carbons in order to a) to prevent the formation of an ignitable or explosive mixture with the organic carbonates contained in the electrolyte (e.g. dimethyl carbonate, ethyl methyl carbonate) and b) to reduce the water content of the atmosphere as much as possible and to prevent an exothermic reaction of the fluorine-containing conducting salts of the electrolyte and the lithium, which is still partially deposited in metallic form on the graphite electrode, with the otherwise existing atmospheric humidity and to recover the volatile electrolyte components in anhydrous form.

[0110] Inerting with nitrogen is preferably carried out in a functional integration with cooling of the comminution chamber by injecting liquid nitrogen. The expansion of the liquid nitrogen removes heat from the comminution chamber, thus further reducing reactivity in the comminution chamber.

[0111] In one embodiment of the invention, the gas-tight and preferably vacuum-tight comminutor is directly connected to the electrolyte recovery system. This allows the organic solvents escaping during cell opening to be directly evaporated under vacuum. The heat of comminution contributes to the energy required for the evaporation enthalpy, while the comminution chamber is cooled directly by removing the evaporation enthalpy. Comminution can be performed more intensively and rapidly without fear of negative side effects due to temperature-induced conversion of the conducting salt to hydrogen fluoride.

[0112] In a preferred embodiment of the invention, comminution is carried out under vacuum. The explosion protection in this embodiment is simple and very effective. At the first level, the constant evacuation eliminates the oxygen needed for ignition. At the second level, an explosion typically results in a maximum volume expansion by a factor of 10 relative to the initial pressure. At an absolute pressure of less than 100 mbar, the maximum achievable explosion pressure is 1 bar, which corresponds only to the ambient pressure and is therefore harmless. 4. Selective, non-thermal deagglomeration of the black mass components - Step 18:

[0113] After crushing, the so-called black mass components of the battery are deagglomerated by introducing mechanical energy into a deagglomeration device B. This can be achieved, for example, by mixing in a deagglomeration device.

[0114] "Black mass" refers to the powdered raw material concentrate recovered from the coatings of the electrodes (anodes and cathodes). In addition to the current collector foils made of copper and aluminum, the battery electrodes consist primarily of metals such as lithium, manganese, cobalt, and nickel, as well as graphite and a binder. The shredded battery material is treated to produce black mass, which contains a large amount of these metals. The black mass consists primarily of the coating materials of the electrode foils and small amounts of aluminum, copper, and mostly polyethylene, as well as other impurities from the recycling process. The black mass contains valuable raw materials such as lithium, graphite, cobalt, copper, nickel, and manganese.

[0115] The deagglomeration of cathodic active materials takes place under such high energy input and such a process time that the median value x 50the particle size distribution after de-agglomeration is smaller than four times (preferably twice) the x 50 the particle size distribution of the industrial starting product of the cathodic active material.

[0116] As an exception, deagglomeration occurs for batteries with active materials with a median value x 50 the particle size distribution <5 µm, for example based on lithium iron phosphate chemistry, to 10-20 times the median value x 50 the particle size distribution of the industrial starting product of the cathodic active material.

[0117] Furthermore, the deagglomeration is carried out in such a way that the maximum particle size of the coating components after deagglomeration does not exceed an average of 100 µm (preferably 50 µm).

[0118] This step opens interparticle pores, facilitating the evaporation of the electrolyte's low-boiling components and residual water from underwater comminution by reducing pressure losses and diffusion resistance through the pores and increasing the free particle surface area. The Stefan tube effect, which occurs during evaporation in the pores, is minimized. Furthermore, the effect of capillary condensation, which counteracts evaporation, is reduced by reducing the intraparticle pores.

[0119] In the case of faulty, incomplete deactivation due to deep discharge, electrolyte removal, or only temporary deactivation due to prior freezing, the deagglomeration step also separates the galvanic elements and mixes them at the particulate level. The chemical potential differences are thus resolved in a very small space with an infinitesimally small energy exchange. Localized heating of the active material due to microshort circuits and the subsequent spontaneous combustion of the material can thus be prevented.

[0120] In contrast to finer comminution, in which all components of the battery would be stressed and crushed, the deagglomeration of the active material here occurs selectively through intensive mixing. The agglomerates of the coating materials are primarily crushed, while the elastic aluminum and copper foils are not crushed to the same extent, and the heavy components are not crushed, but rather act as autogenous grinding media.

[0121] The specific power input per kg of black mass is preferably at least 50 kW / t (= 50 J / (s*kg) = 0.050 kW / kg), where the specific power input L is calculated as follows L=(P_Desagglo) / (m_Schwarzmasse) where P_Desagglo is the power consumption of the deagglomeration unit and m_Blackmass is the mass of the black mass.

[0122] This selective, non-thermal deagglomeration of the black mass enables the clean separation of the so-called black mass (the separated coating of the battery electrodes, which contains valuable precursors or raw materials) from the remaining battery components. Fine to ultrafine screening requires a deagglomerated black mass to separate small metal particles (Cu, Al, Fe). The smaller the average particle size of the black mass or the median value (x 50 ) of the particle size distribution of the black mass, the finer the sieving can be with high yields and high purity and the more small metal particles can be separated from the desired black mass by sieving.

[0123] In addition, deagglomeration enables the subsequent separation of the graphite through screening, flotation, and / or heavy liquids. This separation is also a prerequisite for efficient metallurgical processing, as higher concentrations of the valuable metals nickel and cobalt result in better plant utilization. It also enables the recovery of the graphite at a high value-added level, preferably as battery graphite with very high purity. 5. Electrolyte removal and drying of residual water - Step 20:

[0124] Beginning with or immediately after comminution, the electrolyte content of the electrochemically inactive or inactivated cell components is rapidly reduced to prevent the formation of an ignitable or explosive mixture during subsequent processing or in storage and shipping packaging. This means that the resulting components no longer pose a fire or explosion hazard.

[0125] Preferably, the electrolyte removal is functionally integrated with the deagglomeration and carried out in parallel in the same apparatus.

[0126] Particularly preferred is additional drying out of the wet crushing or other moisture introduced.

[0127] This targeted removal of the electrolyte is achieved, for example, by a) Vacuum drying - step 22 - at a temperature below 80°C to minimize HF formation or at an elevated temperature above 80°C in combination with gas scrubbing of the exhaust gases; the vacuum is preferably provided by a dry-running vacuum pump, but the use of other types of vacuum pumps is also possible; b) contact drying - step 24 - continuously by contact with a rotary kiln having a temperature above 120 °C, preferably in a heated container filled in batches, in which mixing is ensured by rotation or mixing tools; contact drying can be combined with vacuum drying; c) convection drying - step 26 - with inert gas or preferably pre-dried ambient air in such an excess that no explosive mixture can form; d) Radiation drying - step 28 - by infrared radiation and / or UV radiation and / or microwave radiation; radiation drying may be combined with vacuum drying and contact drying; e) or a combination of these drying methods 22, 24, 26, 28.

[0128] In one embodiment, drying is carried out in functional integration with thermal decomposition of the binder at a temperature of 450-1000 °C in preparation for easy separation of the electrode coating.

[0129] Optionally, recondensation - step 29 - of the electrolyte solvents takes place.

[0130] In addition, optional (preferably re-separable) reagents for fluorine depletion / reaction (e.g. limestone granules) are used.

[0131] Preferably, in the area in which the drying process is carried out, the flow cross-section, preferably up to the dedusting unit into which the drying gas is discharged, is selected to be so large that the flow velocity is on average below 5 m / s in order to avoid contamination and to relieve the load on components of the dedusting unit, such as filters.

[0132] Preferably, the electrolyte recovery process is carried out at least partially in a mobile long-term drying vessel. This drying vessel is filled directly from a comminution unit or from the deagglomeration device and evacuated together with them. 6. Gas purification - Step 30 - in combination with solvent recovery - Step 31:

[0133] To prevent the resulting drying gases, which may contain fluorine compounds, including hydrogen fluoride, and organic carbonates and their decomposition products, from being released into the environment in an untreated state, they are purified. This is preferably achieved through a combination of the following processes: a) gas scrubbing with a preferably alkaline solvent (e.g. NaOH, KOH, milk of lime) to bind the resulting hydrogen fluoride, preferably by means of a jet scrubber which provides a vacuum on the suction side; b) Adsorption of the organic components on activated carbon, optionally coupled with chemisorption of hydrogen fluoride; c) Thermal afterburning; d) recompression in pressure vessels (e.g. gas cylinders), removal and central gas processing or gas combustion; e) Condensation - step 29 - of the organic components (by cooling or freezing) in combination with the recovery of the low boilers of the electrolyte. 7. Transport in gas-tight and dust-tight containers - Step 32:

[0134] The resulting inactivated components should preferably be transferred as little as possible to avoid dust and gas exchange with the environment. The safest way to store shredded batteries is in a transport container that contains no oxygen or moisture and in which the shredded material cannot come into contact with moisture or atmospheric oxygen.

[0135] Therefore, the dried battery materials are preferably packaged in a dust- and gas-tight manner. This prevents any carcinogenic components (e.g., cobalt and nickel oxides) and fluorine components from escaping during subsequent transport and storage. Furthermore, the bulk material is protected from the influence of the ambient atmosphere and the associated water ingress.

[0136] This happens, for example, through: a) vacuum packaging; b) packaging under inert gas; c) a gas-tight, vacuum-tight container which maintains a vacuum and to which a discharge unit can be connected in a dust-tight manner; d) a gas-tight, vacuum-tight container which maintains a vacuum and which has a discharge unit to which another container can be connected in a dust-tight manner; e) a container, such as one of the containers described above, which has a stirring unit; f) a container, such as one of those described above, which can be connected to a vacuum pump; g) a container, such as one of the containers described above, into which a vacuum pump is integrated; h) a container maintaining an inert atmosphere, in particular - about tightness and / or - via active sensor-controlled inerting with inert gas, in particular pressure-controlled (preferably at overpressure) or oxygen-controlled.

[0137] In a preferred embodiment, the shredded material can be dried in the gas-tight transport container by convection, heat conduction, or vacuum. This can reduce the drying time in the combined mixing-drying unit. The heat can be introduced, for example, via a double jacket.

[0138] This portable mixer, referred to here as Transport Mixer C, is preferably also a mobile long-term dryer. It allows for a long drying time.

[0139] It is advantageous because it is not limited by diffusion, has a higher recycling efficiency due to the recovery of organic carbonates and only low gas flows, so that it achieves efficient condensation through improved heat transfer and only low nitrogen consumption through a carrier gas cycle.

[0140] It is also advantageous because it allows the evaporation enthalpy to be supplied over a long period of time and thus at a low temperature level.

[0141] It is preferably designed to utilize the waste heat from other units and processes.

[0142] The low temperature level enables a high coefficient of performance of a potential heat pump. Preferably, heat is fed in from the discharge of the batteries or the deactivation step.

[0143] The low temperature level is advantageous because fewer undesirable side reactions occur due to the decomposition of conductive salt and organic carbonates and additives.

[0144] The transport mixer C thus represents a long-term mixer that relieves the load on the deagglomeration device during the drying period. The deagglomeration device only needs to be operated until the desired deagglomeration is achieved. The remaining drying time until the drying criterion is reached takes place in the more economical long-term dryer. 8. Emptying at the point of further processing - Step 34:

[0145] During transport and storage, the battery shredded material can compact into cohesive bulk material and subsequently form bulk material bridges, making controlled, low-dust emptying without human intervention difficult. The transport mixer loosens the material, making it contamination-free for conveying and dosing. In one embodiment, the transportable mixer includes a filling and dosing unit for mobile, safe emptying.

[0146] In the following, a module D preferably carries out the steps of heavy material separation, magnetic separation, non-ferrous metal separation, screening, secondary shredding and sifting for the processing and separation of the individual recyclable material fractions.

[0147] After decentralized processing, the packaged product can be safely transported to a larger-capacity processing module. However, this processing module can also be used decentrally to further separate the inactive battery fragments into the various recyclable material streams: aluminum, copper, separator, and a powder fraction enriched with active materials / transition metals on-site. 9. Heavy goods separation - Step 36:

[0148] Furthermore, a heavy material separation is preferably provided, which is carried out, for example, ferromagnetically and / or as a screening process. 10. Light fraction separation - Step 38:

[0149] Furthermore, a light fraction separation is preferably provided, which is carried out, for example, as a screening process, preferably combined with hard part separation. 11. Separation of the coating from current collector foils - Step 40:

[0150] Furthermore, a separation of the coating from current collector foils is preferably provided, wherein preferably for the targeted processing of the active materials and the aluminum and copper, the coating containing the active materials is separated from the current collector foils containing aluminum and copper.

[0151] Preferably, the separation of the coating of the current collector foils comprises the steps of comminution, for example by means of a cutting mill, optionally combined with screening, wherein the screening is preferably air-assisted, and screening of the already separated and deagglomerated coating. 12. Refilling and compacting if necessary - Step 42:

[0152] Furthermore, refilling and, if necessary, compacting of the previously obtained materials is preferably provided. 13. Separation of anodic black mass and cathodic black mass - Step 44:

[0153] Furthermore, a separation of anodic black mass, in particular graphite, and cathodic black mass is preferably provided.

[0154] The aforementioned process steps 36, 38, 40 can also be carried out in reverse order.

[0155] Process steps 34, 36, 38, and 40 are preferably carried out in a dust-free manner. The sealing mechanisms commonly used in conventional recycling machines are considered disadvantageous for the inventive reprocessing of lithium-ion batteries, as harmful dust could enter the environment. Therefore, the invention preferably provides for dust-tight processing. Therefore, process steps 34, 36, 38, and 40 are preferably carried out in a dust-tight and preferably gas-tight manner. One embodiment provides for the use of closed air circuits.

[0156] In a preferred version, the treatment module D can therefore be designed so that it operates under negative pressure in certain areas, preventing the escape of gas components from the system, and in certain areas under positive pressure, only 10 ppm of the electrolyte's low-boiling components can be measured directly on the machine casing. This prevents the escape of hazardous battery components and hazardous reaction products of battery components.

[0157] The transport mixer C, which serves as a mobile long-term dryer and mixer, preferably comprises one or more interchangeable vacuum dryers. An increase in drying capacity is achieved by preferably increasing the number of transport mixers, in particular by connecting several lines of such transport mixers C in parallel.

[0158] The Transport Mixer C enables dust-tight transport and automatic emptying of the cohesive bulk material. A mixing unit in the transport container prevents the risk of compaction due to its own weight and transport movements, thus preventing difficult-to-remove blockages at discharge points.

[0159] In a process envisaged according to an embodiment of the invention at drying temperatures > 80 °C, the hydrogen fluoride- or HF-containing exhaust gases can be removed via a gas scrubber. However, further hydrogen fluoride (HF) is formed (among other substances) in the warm intermediate product, which is preferably not released into the environment, especially not in an uncontrolled manner. It is preferred that the material does not come into contact with atmospheric moisture and oxygen in the warm state. Further reactions can thus be (largely) prevented.

[0160] In Transport Mixer C, the material to be ground can settle, cool, and react completely in a long-term vacuum dryer while connected to a gas scrubber. The settling process advantageously does not require temperature limitations.

[0161] In the transport mixer C, reagents such as water, lime and / or milk of lime are preferably slowly added to react conductive salts such as lithium hexafluorophosphate (LiPF6) and potentially metallic lithium.

[0162] One embodiment provides for drying at higher temperatures, preferably 50 °C to 240 °C, under vacuum with gas scrubbing and then allowing the material to be dried to cool in the long-term dryer (possibly connected to the same gas scrubbing).

[0163] A further embodiment provides that the binder is decomposed at higher temperatures, preferably 500 °C to 700 °C, with gas scrubbing and then allowed to decay in a long-term dryer.

[0164] Another embodiment provides for decentralized electrolyte separation without gas scrubbing. This is followed, preferably, by centralized high-temperature drying in the same reactor or transport mixer C to remove high boilers and conductive salts at a temperature above 80°C, preferably with centralized gas scrubbing.

[0165] The Transport Mixer C enables a significant reduction in environmental contamination with carcinogenic dust through the transport of a large volume and defined coupling mechanisms. For example, 5 tons, preferably 10 tons, and particularly preferably 20 tons, can be filled, transported, and emptied in a defined manner in a transport mixer. In contrast, a conventional big bag as a transport container can only transport 0.5-1 tons of battery shredded material. The number of filling, loading, and emptying processes involving toxic materials can thus be carried out more precisely and reduced by a factor of 40.

[0166] Overall, the invention improves on the state of the art, in which deagglomeration of active materials is achieved by thermal or chemical destruction of the binder. However, this thermal decomposition is energy-intensive and releases, among other things, fluorine-containing exhaust gases that must be treated by gas scrubbing. Dissolving the binder in conventional chemical processes entails the consumption of chemicals. Conventional non-selective comminution processes, in which the entire ground material is comminuted to the same limiting final grain size - defined, for example, by an outlet sieve - lead to heating of the components, the comminution of which requires a higher energy input. The high temperatures of these components, e.g., metal pieces, can lead to damage during filling into plastic containers and, when in contact with binder and electrolyte components, can release toxic exhaust gases such as hydrogen fluoride.

[0167] In addition, these conventional non-selective comminution processes show a disadvantageous enrichment of sieve cuts <0.5 mm with electrode foil components, from which this fraction of the so-called black mass cannot be cleaned by classification.

[0168] The present invention, in contrast, provides for the decentralized shredding of deactivated batteries in gas-tight shredding machines with decentralized electrolyte separation. Advantageously, the resulting fractions are no longer highly flammable and can be transported safely with less effort and under fewer requirements. After the decentralized processing according to the invention, potentially hazardous waste is converted into several recyclable material streams. These recyclable materials can be transported across national borders and can be further processed particularly efficiently. The process is particularly advantageous and sensible from an economic and ecological perspective. Furthermore, oxidative processes can be prevented. The invention substantially reduces the risk of deflagration and / or release of the solvent contained in batteries.

[0169] Furthermore, the following advantages can be achieved thanks to the invention: The invention enables efficient, pure, and energy-saving separation of valuable materials such as cobalt, nickel, lithium, and graphite. Thermal pretreatment of the batteries to be recycled is avoided. Underwater comminution of the batteries to be recycled is avoided. The invention achieves a high yield of active material. The recycling process according to the invention is cost-effective, both in terms of investment and running costs. The structure of the active material is retained. There is no thermal conversion of the active material. Breaking up the agglomerates prepares for clean separation of the graphite from the cathodic active material, in particular lithium metal oxide and lithium iron phosphate, from the black mass without prior thermal decomposition of the binder. Graphite can thus be recovered economically and ecologically efficiently.Lithium can also be recovered – particularly economically and ecologically efficiently. Aluminum from current collector foils and battery cell casings can be recycled. The high efficiency and high recovery rates combined with low energy consumption result in significant CO2 savings.

[0170] The recovered electrode coating powder mixture has a high specific surface area and is therefore particularly reactive in subsequent hydrometallurgical recycling. The high purity of the resulting products results in high value for these products and enables a high selling price.

[0171] The invention avoids a wet intermediate product and achieves an intermediate product that is more easily separable than wet intermediate products.

[0172] The invention can be used advantageously in the processing of scrap materials from battery electrode production, in the processing of scrap materials from battery cell production, in the processing of scrap materials from battery production, in the recycling of aged primary and secondary lithium batteries, e.g. from power tools, stationary energy storage systems, industrial storage systems and e-bikes.

Claims

[1] Recycling process for components of electrochemical energy storage devices, namely batteries with electrodes having electrode carrier foils and an electrode coating applied thereto, comprising the steps a) comminution (16) of battery material, such as production waste arising from the production of batteries, active and deactivated batteries or battery cells, into battery comminution material comprising particles of the electrode carrier foils and particles of the electrode coatings, b) mechanical deagglomeration (18) of the particles of the electrode coatings contained in the battery crushing material, characterized by , that c) the step of mechanical deagglomeration (18) is carried out for such a long time and / or intensively until the maximum size of the particles of the electrode coatings no longer exceeds 100 µm on average by mass, and d) the electrode coatings are comminuted to a particle size distribution such that the average diameter of the particles of the electrode coatings after mechanical deagglomeration is at most 1 / 10 of the average size of the particles of the electrode carrier foils, based on the maximum Feret diameter of the particles of the electrode carrier foils. [2] Recycling process according to claim 1, characterized by that the particle size distribution of the cathodic electrode coatings after mechanical deagglomeration (18) has a median value x 50 which is less than four times the median value x 50 the particle size distribution of the cathodic active material contained in the cathodic electrode coatings in an electrode to be recycled is less than 10 to 20 times the median value x 50the particle size distribution of the cathodic active material contained in the cathodic electrode coatings in the electrode to be recycled during the recycling of lithium iron phosphate batteries. [3] Recycling process according to claim 1 or 2, characterized by that the mechanical deagglomeration (18) is carried out with a specific power input by means of a deagglomeration device (B) for a period of at least one minute with at least 50 watts per kilogram of battery active materials contained in the shredded material. [4] Recycling process according to one of the preceding claims, characterized by the further step following the mechanical deagglomeration (18) of separating the particles of the electrode coatings from the dried comminution material by screening and / or sieving. [5] Recycling process according to one of the preceding claims, characterized bydrying (20) or recovery of solvent contained in the electrolyte of the battery, preferably organic solvent, in a machine. [6] Recycling process according to claim 5, characterized by that the drying (20) is used to dry out coolants or extinguishing agents, for example water, from a wet comminution (16) preceding the drying (20). [7] Recycling process according to one of the preceding claims, characterized bythat the steps of comminution (16) and drying (20) are carried out in a combined and explosion-proof manner in a drying chamber of the machine in which negative pressure or vacuum prevails, wherein explosion protection is provided by monitoring the pressure in this drying chamber and preferably the pressure resistance of the machine is determined in such a way that in the event of an explosion the pressure increase in the machine leads to a maximum of forces acting on the machine which can be tolerated by the machine, in particular that the operating pressure in this drying chamber is in the range from one twentieth to one fifth of the pressure resistance of the machine. [8] Recycling process according to one of the preceding claims, characterized bythat the duration of drying (20) during operation is determined and controlled as a function of a combination of measured values ​​of the proportion of volatile organic carbon in the drying gas and the absolute pressure and / or the rate of change of the absolute pressure in the drying chamber. [9] Recycling process according to one of the preceding claims, characterized by that the galvanic elements of the batteries are deactivated by deep electrical discharge before shredding. [10] Recycling process according to one of the preceding claims, characterized by that the materials to be recycled are components of batteries that were once electrically charged and then deactivated, whereby the deactivation is carried out by a) Deep discharge and / or b) removing the electrolyte by vacuum drying, preferably at a pressure of 0 to 600 mbar, preferably at temperatures <80 °C and / or c) thermal removal of the electrolyte at temperatures >80 °C and / or d) crushing in aqueous solution and / or e) Crushing into coolant / extinguishing agent and / or f) Crushing / mixing with a binding agent, e.g. lime, lime milk. [11] Recycling process according to one of the preceding claims, characterized by that the materials to be recycled are production waste from the electrode production for lithium-ion batteries or from the lithium-ion battery production, preferably from lithium-ion batteries that have never been electrically charged. [12] Recycling process according to one of the preceding claims, characterized bythat the batteries comprise composite materials of electrode assemblies including electrode carrier foils with electrode coatings and separator foils applied thereto. [13] Recycling process according to one of the preceding claims, characterized by that after shredding, the battery shredded material is stored and transported in a gas-tight and dust-tight transport mixer (C), wherein the transport mixer (C) has: a) a mixing tool for mechanically mixing and loosening the battery shredded material, b) a connection option for an active discharge aid or a permanently installed active discharge aid or a conveyor unit for discharging the battery shredded material and c) means for inerting and / or evacuating the transport mixer (C) and for repeatedly adding gas to the transport mixer (C) when the transport mixer (C) is filled with battery shredded material without generating dust, for releasing gas from the transport mixer (C) and / or for creating a vacuum in the transport mixer (C). [14] Recycling process according to claim 13, characterized by that in the transport mixer (C) the battery shredded material is dried for a long time, for example over a period of more than 30 minutes, whereby a) long-term drying before deagglomeration or b) deagglomeration before long-term drying or c) deagglomeration and long-term drying are carried out simultaneously. [15] Recycling process according to one of claims 13 or 14, characterized bythat drying heat is introduced into the transport mixer (C), for example by introducing a tempering liquid into a double jacket surrounding the drying chamber to temper the walls of the drying chamber and / or by heating a heating jacket surrounding the drying chamber. [16] Recycling process according to claim 15, characterized by that the drying heat is supplied over a longer period of time, for example more than 30 minutes, and at a low temperature level, for example at a temperature below 100°C, preferably below 80°C and particularly preferably below 60°C, preferably the drying heat is supplied by using a heat pump and / or using waste heat from units and processes other than units and processes used in the recycling process. [17] Recycling process according to one of claims 13 to 16, characterized bythat after the crushing and intensive mixing steps, the transport mixer (C) is used for final drying. [18] Recycling process according to one of claims 13 to 17, characterized by that the transport mixer (C) is connected to a drying system. [19] Recycling process according to one of claims 13 to 18, characterized by that the transport mixer (C) is connected via a feed system for the supply of the battery material or via a gas pipe connection to a drying and condensation circuit of a preparation plant for the comminution of the battery material and for electrolyte recovery. [20] Recycling process according to one of claims 13 to 19, characterized by that the transport mixer (C) is protected against explosion by means of an explosion protection device, wherein the explosion protection device a) a device for monitoring the pressure in the drying room, b) a device for monitoring volatile organic carbon in the drying gas, and / or c) has a device for monitoring oxygen in the drying gas and / or drying chamber. [21] Recycling process according to one of claims 13 to 20, characterized by that in the transport mixer (C) the battery shredded material is transported by road, rail and / or ship to a processing location and there connected to a processing plant, in particular to a drying system of the processing plant, and / or emptied into this processing plant. [22] Recycling facility designed for recycling components of electrochemical energy storage devices, namely batteries with electrodes comprising electrode carrier foils and an electrode coating applied thereto, comprising a) a comminution unit (A) for comminuting (16) deactivated or non-electrochemically active battery material, such as production waste arising from the production of batteries, deactivated batteries or battery cells, into battery comminution material comprising particles of the electrode carrier foils and particles of the electrode coatings, b) a deagglomeration device (B) for mechanically deagglomerating (18) the particles of the electrode coatings contained in the battery crushing material, characterized by , that c) the deagglomeration device (B) has a control device which is designed to carry out the mechanical deagglomeration (18) for such a long time and / or intensively until the maximum size of the particles of the electrode coatings no longer exceeds 100 µm on average by mass and the electrode coatings are comminuted to a particle size distribution such that the average diameter of the particles of the electrode coatings after the mechanical deagglomeration (18) is at most 1 / 10 of the average size of the particles of the electrode carrier foils, based on the maximum Feret diameter of the particles of the electrode carrier foils. [23] Recycling device according to claim 22 characterized by a gas-tight and dust-tight transport mixer (C) for storing and transporting the battery shredded material, the transport mixer (C) comprising: a) a mixing tool for mechanically mixing and loosening the battery shredded material, b) a connection option for an active discharge aid or a permanently installed active discharge aid for discharging the battery shredded material and c) means for inerting and evacuating the transport mixer (C) and for repeatedly adding gas to the transport mixer, venting gas from the transport mixer and creating a vacuum in the transport mixer when the transport mixer (C) is filled with battery shredded material without generating dust.

Images