[go: up one dir, main page]

EP4476373A1 - Procédé et installation de recyclage d?éléments de batterie ou de parties de ceux-ci - Google Patents

Procédé et installation de recyclage d?éléments de batterie ou de parties de ceux-ci

Info

Publication number
EP4476373A1
EP4476373A1 EP23719668.8A EP23719668A EP4476373A1 EP 4476373 A1 EP4476373 A1 EP 4476373A1 EP 23719668 A EP23719668 A EP 23719668A EP 4476373 A1 EP4476373 A1 EP 4476373A1
Authority
EP
European Patent Office
Prior art keywords
fraction
separation
stage
liquid medium
shredder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23719668.8A
Other languages
German (de)
English (en)
Inventor
Robert JÜTTNER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reelements GmbH
Original Assignee
Reelements GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Reelements GmbH filed Critical Reelements GmbH
Publication of EP4476373A1 publication Critical patent/EP4476373A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B09B3/35—Shredding, crushing or cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B09B3/38—Stirring or kneading
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B2101/00—Type of solid waste
    • B09B2101/15—Electronic waste
    • B09B2101/16—Batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the invention relates to a method and a system for recycling battery cells or parts thereof.
  • These cells or parts thereof have, among other things, electrolytes and films provided with a coating, namely cathode films with a coating of cathode material, and anode films with a coating of anode material.
  • the cells or parts thereof have additional components, in the case of lithium batteries, lithium, in the case of NiMH batteries, nickel (nickel hydroxide) and a metal hydride.
  • DE 10 2019 218 736 A1 discloses a method for material-selective disassembly of lithium-ion batteries, in which the components are placed in a container filled with a liquid and comminuted and separated using an electrohydraulic effect.
  • a pulsed current source is used to generate a shock discharge within the liquid within an underwater spark gap between a ground electrode and a high-voltage electrode.
  • This shock discharge separates the coating material of the foils, i.e. the anode material or the cathode material, at least in sections.
  • the films and the coating materials can then be obtained separately from one another and reused.
  • battery cells consist of an anode, a cathode, a separator, an electrolyte and a housing.
  • the anode and cathode are each typically formed by a film provided with a coating.
  • On the anode side this is typically a copper foil (anode foil) coated with graphite as anode material.
  • On the cathode side this is typically an aluminum foil (cathode foil), which is typically coated with a coating, for example with a lithium-nickel-cobalt-manganese mixed oxide (NMC) as the cathode material.
  • NMC lithium-nickel-cobalt-manganese mixed oxide
  • a coating made of LiCoO, NiCoO, LiFePO4 or other known coating materials is applied.
  • the layer thickness of the film coatings is typically in the range of around 50 pm.
  • the electrolyte used in a lithium-ion battery often consists of a conductive salt and a mixture of highly volatile solvents and less volatile solvents, some of which are also solid at room temperature.
  • the conductive salt only has a proportion of a few percent in the electrolyte, for example only one percent by volume.
  • a LiPF 6 lithium hexafluorophosphate
  • lithium ions migrate from the cathode through the separator foil to the anode and are deposited there. During the discharging process, the lithium ions migrate from the anode to the cathode and are integrated back into the cathode material. While the lithium ions are firmly bound in the cathode material, they are bound on the anode side with only low forces and are largely free in the electrolyte.
  • the invention is based on the object of enabling the most efficient recycling of batteries or battery cells, especially lithium-ion batteries (cells) or parts thereof, with the highest possible recovery rate of different valuable materials contained in the cell.
  • the object is achieved according to the invention by a method and a system for recycling battery cells or parts thereof.
  • the battery cells are in particular cells of a lithium-ion battery.
  • the advantages and preferred configurations listed below with regard to the method can also be applied analogously to the system and vice versa.
  • the system has a shredding stage, preferably with a mechanical shredder, which ensures mechanical pre-shredding of the cells. This is, in particular, wet shredding using a liquid medium. A (wet) shredder faction is available at the exit of the shredder stage.
  • shredders are generally understood to mean devices with the help of which mechanical shredding devices, such as grinders, shearing mills, cutting mills, hammer mills, etc. are carried out. In the broader sense, this also includes rotary shears, guillotines, etc.
  • the films contained in the shredder fraction preferably have a size in the range from 0.3 cm to 10 cm. This size is particularly suitable for the downstream electro-hydraulic separating device.
  • the system has a pre-separation stage with a mechanical separator, which is designed in particular as a stirrer.
  • the shredder fraction is used in particular together with the liquid Medium in this mechanical separator is flushed under the influence of mechanical energy with the help of a liquid medium, in particular the liquid medium from the shredder stage, which is hereinafter referred to as process water without limiting generality.
  • process water without limiting generality.
  • the mechanical action in combination with rinsing with the process water achieves several advantages: On the one hand, there is an advantageous separation of the films, which are still tightly packed in the cell. This means that the surfaces of the films are more accessible in the subsequent process steps and the subsequent separation and recycling steps can therefore be carried out with less effort and more efficiently.
  • rinsing - in the case of lithium-ion batteries - also absorbs the unbound lithium or ions in the process water.
  • a wet separator fraction This contains the process water with the components it contains as well as the shredded films that are at least partially still provided with the coating material.
  • This separator fraction is subsequently fed to at least one further separation stage and further processed there. Specifically, it is fed to an electro-hydraulic separating device, such as that from
  • the mechanical separator is preferably designed as a stirrer which has an agitator.
  • the stirrer generally comprises a container into which the shredder fraction is introduced.
  • the agitator rotates within the container while simultaneously introducing the liquid medium, which is sprayed in, for example.
  • the container is at least partially filled with the process water, so that the stirring takes place directly in the process water.
  • the stirrer easily introduces mechanical energy, which leads to the desired separation of the anode material from the anode foils. This also supports the washing out of the lithium.
  • the mechanical movement of the agitator leads to the desired separation of the films in a particularly efficient manner.
  • a stirrer with an agitator other combined rinsing and separating devices are also possible, for example a rotating drum can be provided and/or the process water is jetted onto the shredder fraction using high pressure through appropriate nozzles, so that the desired separation and rinsing is achieved by the jet pressure of the water.
  • the mechanical separator is preferably arranged directly below the shredder, so that the shredder fraction can enter the mechanical separator from above.
  • the residence time of the shredder fraction within the mechanical separator is typically in the range of a few minutes, for example 20 seconds to 5 minutes.
  • the wet separator fraction is dewatered, for which at least part of the liquid medium with the components contained therein (particles and dissolved substances) is separated off. After dewatering, a dewatered separator fraction is available for further treatment specifically in the electrohydraulic separating device.
  • the particular advantage of this dewatering is that, among other things, the ions contained in the process water, such as lithium ions, are removed, so that the proportion of these conductive elements is reduced for the subsequent process step.
  • a sieve device is used through which the process water can pass and the dewatered separator fraction remains.
  • dewatering takes place via a conveyor device, specifically a screw conveyor, via which the separator fraction is transported to the subsequent recycling stage.
  • the conveyor device is in particular inclined so that the process water can drain downwards against the conveying direction and be collected there. This achieves particularly simple and efficient drainage without the need for an additional drainage device.
  • components contained therein are recovered from the separated process water (liquid medium).
  • lithium and/or anode material is recovered from the separated process water.
  • a suitable treatment device for the process water (liquid medium) which is preferably as treated process water is (re)fed to the mechanical separator (e.g. stirrer) and in particular to the shredder stage as the liquid medium.
  • a portion of the separated process water is fed to the treatment device either continuously or repeatedly via a branch line.
  • the entire separated process water is continuously fed to the treatment device.
  • the pre-shredding in the shredder stage is preferably carried out in a liquid medium.
  • only dry pre-shredding takes place without adding a liquid medium.
  • the submission of a correspondingly amended claim 1 without liquid medium in the shredder stage, in which the cells are dry-shredded in the shredder stage, remains reserved.
  • either the liquid medium is sprayed into the pre-shredding system, i.e. specifically the shredder, or it is filled with the liquid medium.
  • This pre-shredding in a liquid medium generally water or an aqueous solution, has the advantage that the released electrolyte components and, for example, free (lithium) ions are immediately bound.
  • This wet shredding process has the following additional advantages over conventional, dry shredding processes:
  • operation preferably takes place at room temperature, whereas dry shredding processes usually require high temperatures of 80 °C or more to separate the electrolytes from the gas phase.
  • the liquid medium is generally preferably water. This is fed to the shredder stage in particular continuously.
  • the water is preferably removed from the shredder together with the shredder fraction and fed to the mechanical separator as a wet shredder fraction.
  • Shredding and/or pre-separation in the pre-separation stage continue to preferably take place at ambient temperature. Neither active cooling by a cooling device nor active heating by a heating device is provided.
  • a large amount of liquid medium in particular water, is preferably used for the mechanical separator and in particular for the shredder stage.
  • the proportion by weight of the water is preferably at least a factor of 10, more preferably by at least a factor of 30 and in particular by at least a factor of 50 greater than the proportion by weight of the cells or parts of the cells. This large amount means that the above-mentioned advantages of wet treatment are achieved particularly well.
  • Shredding is preferably carried out under water, i.e. the material to be shredded is completely immersed in a water bath.
  • the same preferably also applies to the further treatment, in particular stirring, in the pre-separation stage.
  • a total of a wet shredder fraction is removed from the shredder stage and preferably fed directly to the pre-separation stage and the mechanical separator without further treatment.
  • the ratio of water to the shredded portions of the cells is preferably the same as that stated above for the shredding stage.
  • Process water is therefore preferably constantly supplied to the shredder stage and removed again in the same amount together with the shredded portions and fed to the pre-separation stage as the wet shredder fraction.
  • an expedient design provides that the batteries/cells are brought to a defined state of charge before the battery and cells are shredded, i.e. in particular before the shredding stage.
  • a charging process for the battery is provided.
  • the defined state of charge is, for example, at least 30%, at least 50%, at least 75% or at least 90% or 100% of a maximum state of charge.
  • SOC State of charge
  • State of charge (SOC) is generally understood to be the current capacity of a battery as a percentage of its maximum capacity.
  • the maximum capacity of a battery indicates the maximum amount of electrical charge that the battery can store. It is typically given in amp hours (Ah).
  • a dewatered shredder fraction - is fed in a (first) separation stage to the already mentioned (first) electro-hydraulic separation device .
  • This generally has a bath filled with a liquid medium (process water) into which the dewatered separator fraction is introduced.
  • the separating device is constructed in particular according to DE 10 2019 218 736 A1. It has a ground electrode and a high-voltage electrode, which are controlled in a suitable manner so that regular shock discharges are generated. In addition to shredding the introduced fraction, these also lead to the separation of the coating material from the film.
  • the coating material can be specifically removed either from the anode foil or from the cathode foil.
  • the corresponding coating material is therefore typically only separated from one film material. As mentioned above, this is preferably the anode material, specifically graphite. At the end of the first separation stage there is a first separation fraction.
  • this first separation fraction which is in particular a wet fraction, is separated into a coarse fraction and a fine fraction.
  • the coarse fraction has coarse film parts and the fine fraction has the separated coating material as well as other fine parts, such as film parts. These parts of the fine fraction are contained in particular in the process water.
  • the two fractions (coarse fraction and fine fraction) are then further processed separately.
  • the two different film fractions of the coarse fraction, which are obtained in the first separation stage were separated from each other and the film fraction, which still has its coating, i.e. specifically the cathode film with the cathode material (e.g. NMC), is fed to a second separating device in a second separation stage, for which in particular an electrohydraulic (second) separating device is used.
  • a second separating device in a second separation stage, for which in particular an electrohydraulic (second) separating device is used.
  • This is basically constructed similarly or identically to the first electrohydraulic separating device, with preferably only the process parameters being changed and set in such a way that the cathode material is separated from the cathode foil.
  • the cathode material specifically NMC
  • NMC is separated from the previously separated cathode foil fraction and preserved in great purity. This is subsequently recovered from the process water.
  • dewatering in particular also of the coarse fraction, with subsequent sorting into the two film fractions is preferably provided.
  • sorting can also be carried out wet without prior drainage.
  • a centrifuge is preferably used to dewater the coarse fraction.
  • parts of the fine fraction in the process water and/or the second separation fraction i.e. especially anode particles (graphite) and/or cathode particles (NMC)
  • a further comminution stage and a (further) comminution device which is formed in particular by an electro-hydraulic separation device.
  • a crushed fine fraction is obtained.
  • the parts of the fine fraction or parts of the second separation fraction are again fed to the previous separation stage, in particular to the previous electro-hydraulic separation device.
  • these parts are preferably fed to an additional, further shredding device, specifically a further electro-hydraulic separating device.
  • the parts are in particular the rough parts of the respective faction.
  • the respective fraction is preferably first classified into different size classes, especially into a coarse fine fraction, a fine fine fraction and a very fine fraction, in order to then only classify the coarser parts, in particular the coarse ones To feed the fine fraction to the (further) comminution stage and to obtain the shredded fine fraction.
  • This embodiment is based on the consideration that the fine fraction of the first separation fraction after the first separation stage (after the first electro-hydraulic separation device) or also the second separation fraction after the second separation stage (after the second electro-hydraulic separation device) are still comparatively large parts (greater than 50pm, in particular greater than 250pm ) of the comminuted particles (anode material / cathode material) to which at least some other components still adhere.
  • a binder such as PVDF or CMC, which holds the individual particles of the anode/cathode material together.
  • this is a so-called carbon black, in particular a type of amorphous graphite, which is electrically conductive and which ensures that the current in the cells is conducted through the coating to the respective film.
  • the proportion of binder or carbon black is, for example, between 2% and 5%.
  • the comminuted fine fraction then preferably has a homogeneous particle size and generally preferably a particle size of less than 50 pm and in particular of less than 40 pm or less than 30 pm.
  • the undesirable adhering components binder and conductive carbon black
  • the particles of the coating material are largely kept pure.
  • one or more of the fractions selected from the fine fraction of the first separation stage, the second separation fraction, the classified fractions obtained or the comminuted fine fraction are fed to a subsequent separation stage.
  • the fine fraction, or one or more of the classified fractions obtained from this or the comminuted fraction(s) obtained are fed to the further separation stage.
  • different types of particles in particular particles of the anode material and particles of the cathode material, are separated and separated from one another.
  • the fine fraction obtained is not sufficiently pure, i.e. in the fine fraction there are not only the particles of one coating material (typically the anode material, graphite) but also particles of the other coating material (typically cathode material, NMC contained.
  • the further separation stage therefore results in a further separation of the two coating materials from each other.
  • the further separation is preferably carried out using a centrifuge or using a so-called flotation process.
  • the particles are generally comminuted to a size that is as uniform as possible, which simplifies the subsequent separation of the cathode and anode particles.
  • a further (third) electro-hydraulic separating device is preferably used as the (further) shredding device.
  • Such an electro-hydraulic separating device crushes the introduced material using the shock waves and is able to reduce the particle size. division to homogenize or to separate different (interconnected) types of particles from one another. Depending on the treatment duration and/or pulse energy, the fractions vary in size. The preferred aftertreatment described here therefore deliberately exploits this comminution function in order to obtain the most uniform particle size distribution possible.
  • the fine fraction prepared, homogenized and comminuted in this way is then preferably dewatered and the different components (types of particles) are separated and separated from one another.
  • downstream comminution by means of the (further) comminution device and on the other hand the downstream further separation stage and in particular their combination, are in turn viewed as independent inventive aspects and the filing of divisional applications in this regard remains reserved.
  • the essential steps for the further shredding stage are:
  • the system has several circuits for the liquid medium, which can also be at least partially combined with one another.
  • a first circuit is provided in which at least the shredder and/or the mechanical separator (stirrer) are integrated.
  • a portion of the graphite and in particular a portion of the lithium is contained in the process water of the first circuit and is recovered from it.
  • the second circuit includes in particular the first separation stage with the electro-hydraulic first separation device and the third circuit includes the second separation stage with the second electro-hydraulic separation device.
  • the latter two circuits are preferably coupled to one another, in particular in such a way that the process water of the third circuit is fed to the second circuit and used there and that the process water is cleaned after passing through the second circuit.
  • FIG. 1 shows a partial representation of a system for recycling battery cells in the area of a shredder and a stirrer, which are integrated in a first process water circuit
  • FIG. 2 shows a partial representation of the system in the area of a first electro-hydraulic separating device, which is integrated in a second process water circuit
  • FIG. 3 shows a partial representation of the system in the area of a second electro-hydraulic separating device, which is integrated in a third process water circuit
  • FIGS. 1-3 Parts of a coherent system 20 are shown in FIGS. 1-3. 1 shows a first section in which the items to be recycled Cells Z, in particular lithium cells of a lithium-ion battery, are subjected to pre-shredding and pre-separation.
  • the system has a shredder 22, a stirrer 24 and a conveyor 26 as essential components.
  • a liquid medium referred to here as process water W
  • a liquid medium referred to here as process water W
  • a processing device 30 for processing the process water W and in particular for recovering components of the cells Z is shown as a kind of black box in FIG.
  • this processing device 30 is used to recover lithium and/or graphite.
  • this device is coupled in after sieve and/or filter stages. The sieve or filter stages are preferably used to filter out all particles larger than 5pm, for example, before processing is carried out using the device. In this, the remaining small particles are removed as well as substances dissolved in the process water, especially (lithium) ions.
  • a wet shredder fraction S1 leaves the shredder 22 together with the process water W, which is fed to the stirrer 24 and then leaves it as the wet separator fraction S2.
  • This dewatered separator fraction S2 is fed to a first electrohydraulic separating device 32.
  • graphite G is separated from the shredded anode foils (copper foils CU).
  • the second section of the system 20 has, following the first electrohydraulic separating device 32, several components for drying/dewatering, sorting and classifying the different fractions.
  • the first separation device 32 is a bath filled with process water W, into which the separator fraction S2 is introduced. In this bath, the separator fraction S2 is treated with shock waves with high pulse energy, with the process parameters being set such that the graphite G is separated from the copper foil.
  • the comminuted and treated separator fraction S2 leaves the first separation device 32 as a first separation fraction T1; specifically, it is pumped out of the bath together with the process water W and fed to a centrifuge 34.
  • the coarse fraction C contains, for example, particles with a diameter greater than or equal to 0.5 cm or greater than or equal to 1 cm.
  • the fine fraction F accordingly has particles smaller than 0.5 cm or smaller than 1 cm.
  • the fine fraction F is subsequently classified and finally dried.
  • the fine fraction F together with the process water W is fed to a sieve device 36 in the exemplary embodiment.
  • the process water W is separated and a coarse fine fraction F1 and a fine fine fraction F2 are sorted out and classified.
  • the coarse fine fraction F1 for example, has pieces of film with a size of greater than 250 pm and the fine fine fraction has graphite or pieces of film with a size in the range of, for example, 50-250 pm.
  • Even smaller components are fed to a filter device 38 as the finest fraction F3 with the process water W. From this, the finest fraction F3 is finally obtained, which in particular has graphite G with a particle diameter of, for example, less than 50 pm.
  • the process water W is conducted in the area of this second section of the system 20 in a second circuit K2.
  • the separated coarse fraction C is fed to the third section, as shown in FIG. This section is used in particular for extraction of NMC i.e. the cathode material.
  • a second separating device 40 is provided, in which the NMC is separated from the cathode foil (aluminum foil).
  • the coarse fraction C is dried in a drying device 42 and the various foil fractions are subsequently separated from one another, for example in an air classifier 44, namely on the one hand a copper fraction CU which contains copper foils and on the other hand an aluminum fraction which contains the aluminum foils AL, which are still coated with the cathode material (NMC).
  • the copper fraction CU also contains the separator foils.
  • the aluminum fraction AL is fed to the second electrohydraulic separating device 40, in which the process parameters are now set such that the cathode material, in particular NMC, is separated from the aluminum foils. Depending on the cell type and cathode coating, other materials are also used and separated accordingly, such as NCA, LFP.
  • the comminuted and treated aluminum fraction AL leaves the second separation device 40 as the second separation fraction T2 together with the process water W and is fed to a further filter device 38. In this, the process water W is again separated off together with a very fine fraction F3 and a coarse fine fraction F1 and a fine fine fraction F2 are separated off.
  • the coarse fine fraction F1 in turn contains particles with a diameter of, for example, greater than 250 pm and the fine fine fraction F2 contains particles with a Diameter between 50 and 250 pm.
  • the fine fine fraction F2 typically consists of at least highly enriched NMC.
  • the finest fraction F3 also consists of at least highly enriched NMC. This is in turn fed to a filter device 38 with the process water W and the fine fraction F3 (NMC) is separated there.
  • this coarse fine fraction F1 is fed to a further comminution device, in particular a third electro-hydraulic separating device 50, in a further comminution stage.
  • a further comminution device in particular a third electro-hydraulic separating device 50
  • further comminution and homogenization of the particles of the coarse fine fraction F1 takes place.
  • any remaining binder components or carbon black are separated off.
  • a crushed fine fraction ZF is obtained.
  • Another of the classified fine fractions F2, F3, in particular the fine fine fraction F2, can also be fed to such a further comminution stage.
  • This further comminution device is preferably followed (in each case) by a further separation stage, for example in the form of a further centrifuge 52.
  • a further separation stage for example in the form of a further centrifuge 52.
  • different types of particles in particular the cathode material, are separated from those of the anode material.
  • NMC proportions of, for example, 10% to 20% are still contained in the graphite fraction. This further separation stage therefore achieves improved varietal purity.
  • Such a further separation stage is preferably also provided for one or more or all of the further classified fine fractions F2, F3. These do not necessarily have to be preceded by another shredding stage.
  • the further comminution stage is alternatively arranged, for example, downstream of the first separating device 32, in particular at a position after a separation of the fine fraction F, which is comminuted (i.e. before classification) and from which the comminuted fine fraction ZF is then obtained
  • Such a further comminution stage is additionally or alternatively also arranged for the treatment of the second separation fraction T2 after the second separation device 40, either directly for the treatment of the second separation fraction or - preferably - for the treatment of one or more of the classified fine fractions F1, F2, F3, specifically for Treatment (only) of the coarse fine fraction F1 and possibly also for the treatment of the fine fine fraction F2. Since the second separation fraction T2 is generally already largely pure, a further separation stage is preferably dispensed with here.
  • the process water is pumped in a third circuit K3 and thus continuously through the various components of the third section.
  • the third circuit K3 is coupled to the second circuit K2.
  • the process water W arising in the filter device 38 is fed to the second circuit K2.
  • used process water W is fed to wastewater treatment.
  • the electrolytes, lithium ions and a portion of the graphite are separated with the process water W at an early stage and are separated in a simple and efficiently obtained from the process water W using the treatment device 30. I.e. Lithium and graphite with a high degree of purity are already being extracted here.
  • the state of charge of the batteries and thus the cells Z is set in a defined manner, in particular the batteries / cells Z are deliberately electrically charged before shredding. This increases the “free” lithium ion content, so that as much lithium as possible is flushed out with the process water W and recovered.
  • stirrer 24 separates the otherwise tightly packed films, which is necessary for the subsequent treatment the electro-hydraulic separating devices 32,40 is advantageous. Overall, this improves the separation efficiency with regard to the separation of the coating material from the respective film in the separating devices 32, 40, whereby the degree of recovery is improved. In the system described here, this is typically greater than 90% for NMC.
  • the dewatering of the wet separator fraction S2 should be emphasized before it is fed to the first separation device 32. This means that the proportion of free lithium ions in the process water W is reduced, which has a positive effect on the operation of the first separation device 32.
  • Vehicle batteries are dismantled (manually, semi-automated or automated), the modules are removed and the remaining components (housing, cables, electronics) are sorted and recycled separately as material streams.
  • Battery modules are measured and classified (usable for “2nd life applications” vs. recycling). Modules to be recycled are further pre-sorted (e.g. according to types, chemical composition, if necessary remaining charge)
  • modules are largely or completely discharged using an unloading device.
  • the electricity is fed back into the grid or used for the recycling plant.
  • entire vehicle batteries may also be discharged without first dismantling the modules.
  • the battery modules are dismantled with the aim of separating the individual fractions (in particular the cells, housing parts, electronic parts) without mixing them as much as possible. Pure dismantling (dismantling) steps can be used (e.g. unscrewing, prying) as well as separating processes (sawing, cutting).
  • the components can remain intact or be damaged; the aim is to avoid mixing. If necessary, loosen existing adhesives, conductive pastes or similar using suitable solvents.
  • the battery modules can also be shredded, for example, in a liquid medium or shredded with very high pulse energy using an electro-hydraulic separating device (e.g. according to DE10 2019 218 736 A1).
  • an electro-hydraulic separating device e.g. according to DE10 2019 218 736 A1.
  • the cells Z are roughly shredded or cut into strips. This exposes the battery foils (anode, cathode) and, on the one hand, separates them from the housing, and on the other hand, the electrolytes are washed out and mostly bound in the water.
  • Lithium is already dissolved in the water at this point and can be recovered. In other processes, lithium remains in the black mass and can only be recovered much later in the process or is lost (in pyrolytic processes)
  • the lithium content in the process water can be specifically adjusted by flow rate and charge status (charged cell Most of the lithium is in graphite as a free ion and dissolves in water; discharged cell: most of the lithium is chemically bound in the NMC and remains in the later black mass). This makes it possible to recycle the lithium in advance by charging it beforehand.
  • rotary shears or a guillotine can also be used:
  • the cells are opened automatically by precisely cutting them open on one or more predefined sides.
  • the material flow consists of the following components:
  • Cathode foils made of aluminum with cathode active material mostly still attached e.g. NMC, LFP, etc.
  • Fine fraction (mainly graphite, with smaller proportions of cathode active material and film particles)
  • the resulting fine fraction is firstly removed and sorted/classified (e.g. by sieving, sink-float sorting, centrifugation, magnetic and/or eddy current separation). This happens in steps D1 and D3.
  • the coarse housing components are sorted out (e.g. by float-sink sorting, magnetic and/or eddy current separation).
  • Housing parts can be sorted out in a higher percentage.
  • the shredded or pre-cut cell materials are rinsed or stirred in water for some time (stirrer 24, essential aspect).
  • Steps C2 and D1 to D6 are connected by a common second process water circuit K2.
  • Advantages 1 to 3 and 5 and 6 from B1 also apply here. However, due to process steps B1 and C1, the concentration of electrolytes, graphite and lithium in this second circuit K2 is lower.
  • the process water W can be circulated for longer without intermediate cleaning; The water cycle represents a second cleaning stage, so that the residual concentration is negligibly low.
  • the coarse fraction C from step C2 (mixture of mainly cathode foils, anode foils, separator foils) is conveyed out of the first separating device 32 continuously or discontinuously (and possibly already separated from the fine fraction, but this is not absolutely necessary).
  • the funding is currently using a conveyor belt, but other methods (e.g. screw conveyor, rinsing using process water) are also possible.
  • the coarse fraction C is pre-dewatered in the centrifuge 34 (different types of centrifuges are possible, discontinuous and continuous).
  • the coarse fraction C is dried in the drying device 42.
  • the degree of drying is adjustable and is selected according to the subsequent sorting. Heat drying, air drying or other methods can be used (stationary or continuous).
  • Dewatering D1 and drying D2 are advantageous in the case of dry sorting D3. They can be left out during wet sorting.
  • Wind sifting (dry or largely dry, wind sifting 44).
  • the coarse fraction C is sorted into different fractions (cathode foil, anode foil, separator, housing residues, etc.) in a single or multi-stage process. If necessary, sub-fractions are formed (e.g. different size classes. There may be intermediate steps, e.g. spherification of films, e.g. using an impact mill or similar.
  • Alternatives to wind sifting are optical sorting (dry or largely dry), magnetic separation, eddy current separation (dry or largely dry), wet Sorting processes (sink-swim separation, flotation) as well as magnetic separation, eddy current separation in water.
  • the fines F of step C2 are discharged and classified continuously or discontinuously using the process water W, for example using a sieve with one or more stages.
  • wet sieving but wet separation table(s), dry sieving (if drying is carried out beforehand), centrifugation, hydrocyclone or similar processes are also possible.
  • the sieve stages also serve for pre-drainage.
  • Combinations of magnetic and/or eddy current separation in a wet medium are also possible, as are sedimentation processes.
  • One or more different fractions with different grain sizes and contents are created.
  • filter devices 38 e.g. vacuum, inclined filter, chamber filter press or others. Filter cakes are created per fraction, the consistency of which can vary in terms of residual moisture (i.e. filter cake consists of/contains mostly the active material of the anode (graphite)).
  • step D5 The various fractions from step D5 are dried.
  • the degree of drying is adjustable and is selected according to the customer's requirements. Heat drying, air drying or other methods are used (stationary or continuous). If necessary, presses or other processes are used to compact and package the material.
  • the “cathode foil” fraction from step D3 is fed to another shock wave system (2nd separation device 40, with low pulse energy), in which the active material (e.g. NMC, LFP, NCO,...) is separated from the electrode carrier (generally aluminum foil).
  • the active material e.g. NMC, LFP, NCO,
  • the electrode carrier generally aluminum foil
  • Steps E1 and F1 to F6 are connected by a common process water circuit.
  • Advantages 1, 2 and 6 from B1 also apply here (3, 4 and 5 are no longer relevant because electrolytes and charge were removed in the previous steps). If process steps B, C and D or parts of them are carried out beforehand, the concentration of electrolytes, graphite and lithium in this 3rd water cycle is very low.
  • the process water can be circulated for longer without intermediate cleaning.
  • step E1 the materials are discharged in one or more circuits and separated into different fractions.
  • the aim is, on the one hand, to enrich the cathode active material (NMC) as high as possible in one or more fractions and, on the other hand, to enrich the carrier film (typically aluminum) in other fractions.
  • Sieve classification is preferred (wet) and, if necessary, centrifugation. Alternatives to this are sieve classification (dry), float-sink sorting, flotation, magnetic sorting (possibly for LFP).
  • auxiliary substances may also be added (e.g. precipitants, e.g. caustic soda, e.g. catalytically active substances). If necessary, these substances will also be added in a previous step or at the beginning of the overall wet process (B1).
  • precipitants e.g. caustic soda, e.g. catalytically active substances.
  • step D4 The various fractions from step D4 are thickened and further dewatered using filter units (e.g. vacuum, inclined filter, chamber filter press or others). Filter cakes are created per fraction, the consistency of which can vary in terms of residual moisture. If necessary, presses or other processes are used to compact and package the material.
  • filter units e.g. vacuum, inclined filter, chamber filter press or others. Filter cakes are created per fraction, the consistency of which can vary in terms of residual moisture. If necessary, presses or other processes are used to compact and package the material.
  • Process water W is the medium for many of the aforementioned process steps. This is reused in separate and/or coupled circuits.
  • process water W from the second separation device 40 (step (F1, F2...) is then used in the first separation device 32 (step (C2, D..)), and preferably subsequently used in the pre-shredding (B1, B2). in order to be able to use the water for as long as possible.
  • the cleaning is carried out with regard to suspended and dissolved substances, in particular:
  • Metals and heavy metals e.g. Li, Al, Cu, Ni, Co, Mn, Fe, etc.
  • Fine and ultra-fine filtration (ultrafiltration, reverse osmosis, high-performance disc filters, etc.)
  • filter materials e.g. blotting paper, fiberglass tiles, fabrics
  • Lithium is recovered from the remaining process water W.
  • the charge state is used to set how much lithium ends up in the process water W (charged Most of the lithium is present as an ion, ie is dissolved out of graphite and electrolyte; uncharged Most of the lithium is bound in the NMC, less is released)
  • the atmosphere above the wet and dry process steps is preferably withdrawn continuously or discontinuously and subjected to measurement and cleaning.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Secondary Cells (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé et une installation (20) pour recycler des éléments (Z) de batterie rechargeables ou des parties de ceux-ci qui présentent un électrolyte, du lithium et des films pourvus d'un matériau de revêtement, à savoir des films de cathode pourvus d'un revêtement constitué d'un matériau de cathode et de films d'anode pourvus d'un revêtement constitué d'un matériau d'anode. Selon ce procédé, les cellules (Z) sont prébroyées mécaniquement lors d'une étape de déchiquetage, en particulier dans un milieu liquide (W), et une fraction de déchiquetage (S1) est obtenue, la fraction de déchiquetage (S1) est ensuite rincée lors d'une étape de préséparation à l'aide d'un séparateur mécanique (24), en particulier un agitateur sous l'effet de l'énergie mécanique et à l'aide du milieu liquide (W), ce qui permet de séparer les films et d'enlever les constituants de la fraction de déchiquetage (S1), tels que l'électrolyte, le matériau de revêtement et le lithium, ces constituants étant accumulés dans le milieu liquide (W), et une fraction de séparation (S2) étant obtenue lors de l'étape de préséparation, puis la fraction de séparation (S2) est soumise à une préparation complémentaire lors d'au moins une étape de séparation.
EP23719668.8A 2022-04-13 2023-04-11 Procédé et installation de recyclage d?éléments de batterie ou de parties de ceux-ci Pending EP4476373A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102022203761.8A DE102022203761A1 (de) 2022-04-13 2022-04-13 Verfahren sowie Anlage zum Recycling von Batterie-Zellen oder Teilen hiervon
PCT/EP2023/059417 WO2023198692A1 (fr) 2022-04-13 2023-04-11 Procédé et installation de recyclage d'éléments de batterie ou de parties de ceux-ci

Publications (1)

Publication Number Publication Date
EP4476373A1 true EP4476373A1 (fr) 2024-12-18

Family

ID=86226511

Family Applications (1)

Application Number Title Priority Date Filing Date
EP23719668.8A Pending EP4476373A1 (fr) 2022-04-13 2023-04-11 Procédé et installation de recyclage d?éléments de batterie ou de parties de ceux-ci

Country Status (7)

Country Link
US (1) US20250038290A1 (fr)
EP (1) EP4476373A1 (fr)
JP (1) JP2025512503A (fr)
KR (1) KR20250004266A (fr)
CN (1) CN118946677A (fr)
DE (1) DE102022203761A1 (fr)
WO (1) WO2023198692A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7742866B2 (ja) * 2023-07-24 2025-09-22 プライムプラネットエナジー＆ソリューションズ株式会社 電池材料の製造方法
DE102023211829A1 (de) * 2023-11-27 2025-05-28 CellCircle UG (haftungsbeschränkt) Verfahren und vorrichtung zur disaggregation von partikelverbunden
CN117712536B (zh) * 2023-12-18 2024-08-16 江苏理工学院 一种废旧新能源汽车动力蓄电池回收利用装置

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4424825A1 (de) 1994-07-14 1996-01-18 Gabler Ing Kontor Luebeck Verfahren zum Entsorgen von entladenen und geladenen elektrischen Feststoff-Batterien
CN205985252U (zh) 2016-08-24 2017-02-22 合肥国轩高科动力能源有限公司 一种用于锂离子电池正、负极材料的回收装置
EP4050701A1 (fr) 2017-05-30 2022-08-31 Li-Cycle Corp. Procédé, appareil et système de récupération de matériaux à partir de batteries
DE102019218736A1 (de) 2018-12-03 2020-06-04 Impulstec Gmbh Verfahren und eine Vorrichtung zur Material selektiven Zerlegung eines Werkstückes mit Anode und Kathode
CN112246835B (zh) * 2020-10-04 2022-03-04 湖南金源新材料股份有限公司 一种废旧锂离子电池的拆解分离方法

Also Published As

Publication number Publication date
WO2023198692A1 (fr) 2023-10-19
DE102022203761A1 (de) 2023-10-19
CN118946677A (zh) 2024-11-12
KR20250004266A (ko) 2025-01-07
JP2025512503A (ja) 2025-04-17
US20250038290A1 (en) 2025-01-30

Similar Documents

Publication Publication Date Title
WO2023198692A1 (fr) Procédé et installation de recyclage d'éléments de batterie ou de parties de ceux-ci
DE102011110083B4 (de) Verfahren zum Wiedergewinnen von Aktivmaterial aus einer galvanischen Zelle und Aktivmaterial-Separationsanlage, insbesondere Aktivmetall-Separationsanlage
EP0652811B1 (fr) Procede de recuperation de matieres premieres provenant de produits usages, collectes et pretries, notamment de piles electrochimiques et d'accumulateurs usages
EP0585701B1 (fr) Procédé pour le traitement des cellules nickel-cadmium ou nickel-hydride
WO2019149698A1 (fr) Procédé de recyclage de batteries au lithium
KR20230038506A (ko) 폐 리튬 이온 배터리의 분해 분리 방법
DE102019218736A1 (de) Verfahren und eine Vorrichtung zur Material selektiven Zerlegung eines Werkstückes mit Anode und Kathode
EP1652253A1 (fr) Procede pour traiter des composants electriques contenant des cations organiques, des solvants non aqueux et du carbone
EP3563446A1 (fr) Procédé de recyclage d'accumulateurs aux ions lithium
DE102015216932A1 (de) Verfahren zum Recycling von Kompositwerkstoffen sowie recycelte Kompositwerkstoffe
DE102018001273A1 (de) Verfahren zum Recycling von Lithium-lonenakkumulatoren
EP4609459A1 (fr) Procédé de recyclage de batteries en métal alcalin et système de traitement de batterie
DE102023201762A1 (de) Verfahren und Anlage zur Gewinnung von Grafit
WO2023110167A1 (fr) Procédé de recyclage de batteries rechargeables et système de traitement de batteries rechargeables
DE102023211829A1 (de) Verfahren und vorrichtung zur disaggregation von partikelverbunden
EP4582570A1 (fr) Préparation de matière noire
WO2023186889A1 (fr) Procédé et installation pour produire du graphite
DE102024108517A1 (de) Verfahren zur Separation einer Elektrodenbeschichtung von einer Stromableiterfolie
WO2023186890A1 (fr) Procédé et système d'obtention de graphite
WO2023186891A1 (fr) Procédé et système d'obtention de graphite
DE102024000111A1 (de) Verfahren zum Direktrecycling von Elektrodenmaterialien aus Schrotten der Herstellung von Lithium-lonen-Batterien
EP4449532A1 (fr) Procédé de recyclage de batteries rechargeables et système de traitement de batteries rechargeables
EP4581180A1 (fr) Procédé de reconditionnement d'accumulateurs d'énergie contenant du lithium

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20240909

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)