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WO2024046889A1 - Procédé de reconditionnement d'accumulateurs d'énergie contenant du lithium - Google Patents

Procédé de reconditionnement d'accumulateurs d'énergie contenant du lithium Download PDF

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Publication number
WO2024046889A1
WO2024046889A1 PCT/EP2023/073322 EP2023073322W WO2024046889A1 WO 2024046889 A1 WO2024046889 A1 WO 2024046889A1 EP 2023073322 W EP2023073322 W EP 2023073322W WO 2024046889 A1 WO2024046889 A1 WO 2024046889A1
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WO
WIPO (PCT)
Prior art keywords
lithium
energy storage
process step
carbon dioxide
containing energy
Prior art date
Application number
PCT/EP2023/073322
Other languages
German (de)
English (en)
Inventor
Lilian Schwich
Paul Sabarny
Original Assignee
cylib GmbH
Rheinisch-Westfälische Technische Hochschule Aachen, Körperschaft des öffentlichen Rechts
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 cylib GmbH, Rheinisch-Westfälische Technische Hochschule Aachen, Körperschaft des öffentlichen Rechts filed Critical cylib GmbH
Publication of WO2024046889A1 publication Critical patent/WO2024046889A1/fr

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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
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • 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
    • 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
    • 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
    • C22B7/007—Wet processes by acid leaching
    • 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

Definitions

  • the present invention relates to a method for processing lithium-containing energy storage devices.
  • the present invention relates in particular to a method by which lithium-containing energy storage devices, in particular lithium-ion batteries, can be processed or recycled.
  • lithium iron phosphate LFP system
  • nickel cobalt aluminum NCA system
  • Lithium on the other hand, will probably continue to be an established component of lithium-ion batteries due to its properties such as low density and lowest standard potential. This results in the need for efficient recycling of lithium.
  • economic and geopolitical factors are driving forces for lithium recycling.
  • WO 2021/226719 A1 describes a hydrometallurgical green chemistry process for recovering one or more metals from a metal-containing material, leaching the metal-containing material with formic acid, obtaining a leachate that contains the one or more metals as one or more metal formates, and the precipitation of at least one of the one or more metal formates.
  • the metal-containing material may be a cathode material for lithium-ion batteries, resulting in Li formate remaining in solution and precipitation of salts containing one or more of the formates Ni, Co and Mn.
  • To the steps may include filtration of the leachate, sulfurization of the retained metal formate salts to produce metal sulfate salts, purification of the filtered leachate by adding lithium carbonate and filtration, dewatering of the purified leachate, and thermal decomposition of the resulting lithium salts to produce battery-grade lithium carbonate.
  • CN109921125 A describes pretreatment procedures for recycling lithium batteries, which includes the following steps: Step 1, disassembling a lithium battery to obtain a positive plate, a negative plate, a separator, a battery case and a cover plate; Step 2, performing pre-grinding on the positive plate and selecting a positive electrode material and a conductive agent; Step 3, performing heat treatment on the positive electrode material; Step 4, mixing the heat-treated positive electrode material with an active mechanical grounding additive to activate the positive electrode material; and Step 5, performing pre-grinding of the negative plate and then placing it in a shaker for separation to select a metal foil material and preparation.
  • CN106505271 A discloses a method for recycling a lithium-ion battery.
  • the method includes the steps of cutting electrode plates removed from the lithium-ion battery and gradually heating and heat preservation in a heating furnace with a gas collection device; placing the electrode plates subjected to heating and heat preservation into a sodium hydroxide solution until an electrode material is stripped from the aluminum foil; directly recycling the aluminum foil, collecting the electrode material at the same time, washing and drying the electrode material, and then uniformly grinding the electrode material in a ball mill; and testing the content of various elements in the electrode material.
  • CN113921931 A relates to a method for recycling lithium carbonate from used lithium-ion batteries, in particular a method for recycling lithium carbonate from used lithium-ion batteries by thermal reduction using carbon.
  • This paper aims to solve the technical problems that the positive and negative electrode materials in the existing black powder from spent lithium-ion batteries are difficult to separate and the lithium resources are difficult to recycle.
  • a discarded lithium-ion battery can be directly crushed and sieved to obtain the black powder under the conditions of no discharge and no disassembly and separation, lithium is largely recycled from the discarded lithium-ion battery while Nickel, cobalt and manganese in the filter residues obtained from the first suction filtration in the first step can be used for the production of a precursor or specifically recycled.
  • the solutions known from the prior art may still have potential for improvement, particularly with regard to efficient recycling of lithium-containing batteries.
  • the problem is solved by a method with the features of claim 1 and claim 2.
  • the problem is also solved by using the method according to the invention for lithium and anode material recovery from lithium-containing energy storage devices.
  • Preferred embodiments of the invention are disclosed in the subclaims, in the description and in the figures, with further features described or shown in the subclaims or in the description or the figures, individually or in any combination, being able to constitute an object of the invention if: The context does not clearly indicate the opposite.
  • the present invention relates to a method for processing lithium-containing energy storage devices, the method having at least the following process steps: i) optionally pre-treating the lithium-containing energy storage device, the pre-treatment comprising at least one of thermal, mechanical and electrical pre-treatment; ii) pyrolyzing the optionally pretreated lithium-containing energy storage device with the release of carbon dioxide and under a carbon dioxide atmosphere with at least partial carbonation of the lithium contained; iii) separating lithium in a separation step; and iv) hydrometallurgical processing of the mixture formed in process step iii) with further carbonation of the lithium contained and with removal of lithium in a further separation step, wherein v) carbon dioxide released in process step ii) is recycled into at least one of process steps ii) and iii).
  • the present invention also relates to a method for processing lithium-containing energy storage devices, the method having at least the following process steps: i) optionally pre-treating the lithium-containing energy storage device, the pre-treatment comprising at least one of thermal, mechanical and electrical pre-treatment; ii) Pyrolyzing the optionally pretreated lithium-containing energy storage with the release of carbon dioxide and under a Carbon dioxide atmosphere with at least partial carbonation of the lithium contained; iii) separating lithium in a separation step; and iv) hydrometallurgical processing of the mixture formed in process step iii) with further carbonation of the lithium contained and with removal of lithium in a further separation step.
  • Reprocessing should in particular be understood as a process that allows raw materials contained in the energy storage to be recovered.
  • an energy storage device usually contains metals or metal compounds that can be used as raw materials to create value.
  • the lithium used in energy storage devices can be recovered using the process described here, although the process is not only limited to the recovery of lithium in a manner understandable to those skilled in the art.
  • anode material such as graphite can also be recovered.
  • lithium-containing energy storage devices are used in particular, which have reached their useful life. Such energy storage devices are also called “End of Life” energy storage devices.
  • energy storage devices are also called “End of Life” energy storage devices.
  • other energy storage devices can also be used, such as faulty production or damaged energy storage devices.
  • the particular advantage of using secondary material as a starting material for the process described here is that lithium is more highly concentrated in energy storage devices than in primary ores, for example. This means that extraction is basically simplified compared to mining and is therefore advantageous. At the same time, lithium is currently not sufficiently recycled, which is why the invention makes a contribution to the recycling of battery raw materials.
  • shredded material, production scrap can be used as lithium-containing energy storage , cells, modules and mixtures thereof can be used.
  • the lithium-containing energy storage device is optionally pretreated, the pretreatment, when carried out, comprising at least one of a thermal, mechanical and electrical pretreatment.
  • the pretreatment serves in particular to prepare the lithium-containing energy storage used for the further process and for the actual recovery of the raw materials, in particular for the recovery of the lithium, and, if necessary, to begin separating some raw materials from the lithium-containing product stream.
  • This product stream is also referred to as black mass and usually contains at least the active material, preferably cathode active material and anode active material, with the corresponding lithium compound.
  • pretreatment can ensure that subsequent process steps are more efficient or possible with greater safety.
  • pretreatment it becomes possible, for example, to remove plastic components or specific other materials such as metals, solvents, WEEE recyclables (waste of electrical and electronic equipment).
  • cabling, control units, such as the battery management system (BMS) or components that can be referred to as heavy fraction, such as the module housing or parts thereof, for example made of iron or aluminum, or contacts, for example made of copper, can also be used
  • the lithium-containing product stream to be treated is separated off.
  • Thermal, mechanical and electrical pretreatment are particularly advantageous as pretreatment. Only one thermal, only one mechanical, only one electrical or a plurality of the respective pretreatments can be carried out in combination simultaneously or one after the other.
  • a thermal treatment in particular a thermal deactivation of the energy storage can take place, so that the subsequent steps can be carried out without safety concerns.
  • the lead charge in particular LiPF 6
  • the lead charge is decomposed during the thermal pretreatment.
  • the decomposition products of the conductive salt are then available for further conversion in the subsequent pyrolysis.
  • the organic components or a proportion of low boilers, preferably solvents can be volatilized and then condensed.
  • solvents in the electrolyte are preferably volatilized and condensed for recovery. Thermal pretreatment can therefore serve both a safety aspect and an already starting separation of the materials in the energy storage device.
  • a mechanical pretreatment can in particular include dismantling an energy storage device.
  • the energy storage device used can be dismantled down to the module level or cell level in order to simplify the further process steps and, if necessary, to remove components such as contacts, housing components and control units from the lithium-containing product stream. It is also possible to use the energy storage to mechanically comminute, such as shredding, for example under protective gas, with the separation of the electrolyte.
  • An electrical pretreatment can in particular include a preferably complete discharge of the energy storage device. This can be achieved purely electrically, using a usual discharge, or through thermal or mechanical treatment.
  • An electrical discharge offers the advantage that the Li ions are stored in the transition metal oxides on the cathode side. Since the cathode material is decomposed into short-chain components during pyrolysis, the lithium in the cathode material is more accessible after pyrolysis than it would be in the anode material. The yield of lithium can thus be improved.
  • method step i) comprises at least one of the following method steps:
  • the method comprises a thermal pretreatment of the energy storage device, which has been dismantled down to the module level and/or cell level, to decompose the conductive salt and to volatilize solvent, wherein in method step ii) shredded material is used as lithium-containing energy storage device, the shredded material comprising cathode material and anode material, whereby the pretreated lithium-containing energy storage device is comminuted between the thermal pretreatment and process step ii).
  • the temperature during the thermal pretreatment is not more than 350 °C.
  • the process further comprises pyrolyzing the optionally pretreated lithium-containing energy storage device with the release of carbon dioxide and under a carbon dioxide atmosphere with at least partial carbonation of the lithium contained.
  • this step can include thermal treatment of the possibly pretreated energy storage, i.e. the lithium-containing product stream resulting from the pretreatment.
  • the energy storage devices to be treated can be directly subjected to thermal treatment or without pretreatment Pyrolysis according to process step ii) are subjected.
  • the product stream from the pretreatment can be used for process step ii), such as shredded material, production scrap, whole cells, modules, but also the untreated energy storage.
  • the lithium-containing energy storage device preferably comprises cathode material and anode material in method step ii). Accordingly, it is preferred not to use any material that contains only minor residues of anode material.
  • the lithium-containing energy storage in process step ii) preferably contains >20% by weight of anode material, particularly preferably >20% by weight of graphite.
  • the lithium-containing energy storage device in method step ii) further comprises the conductive salt and/or its decomposition products.
  • the lithium-containing energy storage device further comprises the current conductors in method step ii).
  • shredded material is used for the pyrolysis to which active material powder from the cathode and anode adheres (so-called “powder-coated shredded material”).
  • the temperature during process step ii) (pyrolysis) is 500 ° C to 700 ° C.
  • This process step serves in particular to at least partially carbonate the lithium contained in the lithium-containing product stream, i.e. in particular to convert the lithium compounds present in the optionally pretreated battery cells into water-soluble lithium carbonate.
  • This enables the carbonated lithium to be selectively washed out later in an aqueous solution without dissolving further components from the active material.
  • Another advantage is the possible combination of leaching with a flotation process to recover the graphite, as described in greater detail below.
  • Lithium fluoride is also preferably formed during pyrolysis, which can subsequently be separated off.
  • the method preferably also represents a method for recovering lithium fluoride from lithium-containing energy storage devices.
  • a reducing atmosphere is important so that the carbonation can proceed undisturbed.
  • the reducing atmosphere can be set by producing CO2 through the pyrolysis of the lithium-containing material and thus releasing it.
  • the active material has materials, such as NMC and the binder, which also release carbon dioxide during pyrolysis under a reducing atmosphere. Accordingly, it can be advantageous if, in this step, the active material containing lithium and having one or more oxygen atoms in its molecular structure and also the binder are present as a carbon-containing or organic material, such as PVDF.
  • a protective gas can be supplied to this process step, such as argon or nitrogen. This means that a suitable atmosphere can be present, although this does not only need to be formed by carbon dioxide. However, according to the invention, the resulting carbon dioxide is also recycled, as will be described in detail later.
  • the carbon dioxide atmosphere optionally also in combination with protective gas such as argon or nitrogen, suppresses undesirable oxidation reactions.
  • the atmosphere also preferably makes it possible for lithium fluoride to be separated off in step iii).
  • the inventors assume that the carbon dioxide atmosphere forms a protective gas atmosphere. Pyrolysis under the carbon dioxide atmosphere leads to the decomposition of binder and the decomposition of the long-chain transition metal oxides into simple transition metal oxides, whereby lithium is released. This pyrolytic change in the feed material can be seen, for example, in the flaking off of powder coatings from the conductor foils (aluminum and copper foils). When the long-chain transition metal oxides thermally decompose under non-oxidizing conditions, the lithium is released from the matrix. Since entire modules/cells are treated in which the electrolyte and conductive salt residues are still present, the yield is particularly high.
  • transition metals such as cobalt, nickel and manganese are not reduced to metallic transition metal in process step ii) pyrolysis and in the thermal pretreatment that may take place.
  • the product stream i.e. the lithium-containing material that has undergone the pyrolysis
  • process step iii lithium is separated off in a first separation step, whereby separation is understood to mean in particular a selective separation of a lithium compound from the residual mass.
  • separation can be done in particular by leaching the product obtained in the steps described above.
  • neutral leaching can take place in an aqueous solution by adding water to the product to be treated. This allows the lithium in the form of lithium carbonate, which was produced by thermal carbonation as described above, to be washed out highly selectively without any foreign substances being carried away. This means that lithium carbonate can be separated in a comparatively clean form and then processed into lithium.
  • fluoride in particular lithium fluoride
  • process step iii fluoride, in particular lithium fluoride
  • neutral leaching for example, only takes place with water, which is an advantage over prior art processes in which acids often had to be used.
  • the introduction of carbon dioxide into the solution is advantageous here, as this creates carbonic acid, which can improve the dissolution of lithium compounds in aqueous solution and thus the discharge of lithium.
  • the carbon dioxide serves to adjust a pH value in the neutral to slightly acidic range, which facilitates selective separation of lithium.
  • the mixture resulting from process step iii), which has been depleted of lithium is further processed hydrometallurgically.
  • the lithium still contained or the lithium compound still contained is further carbonated.
  • This step takes place by separating other substances, in particular metals such as aluminum, iron, cobalt, nickel and manganese, and thus also from remaining lithium.
  • the removal of the respective metals can be achieved by changing the pH value and/or by extracting with organic solvents, as is generally known for hydrometallurgical processes.
  • process step v) it is further provided that carbon dioxide released in process step ii) is recycled into at least one of process steps ii) and iii).
  • the carbon dioxide released in process step ii) can only be recycled into process step ii), the carbon dioxide released in process step ii) can only be recycled into process step iii), or the carbon dioxide released in process step ii) can be recycled into both process steps ii) and iii) and, if necessary, led to further procedural steps.
  • the resulting carbon dioxide When the resulting carbon dioxide is fed into process step ii), it serves to produce a reducing atmosphere and to provide a reagent for carbonation.
  • exhaust gases from the thermal treatment of lithium-based energy storage devices are used to carbonate Li compounds and thus become a central point in the recovery of lithium as a new raw material.
  • CC cycle that is specifically tailored to the process developed here and offers significant synergetic advantages.
  • other particularly gaseous components such as protective gases, for example argon or nitrogen, can also be circulated, which occur in step ii) or are fed in there.
  • protective gases for example argon or nitrogen
  • process step ii) carbon dioxide is used to carry out carbonation of lithium.
  • the resulting carbon dioxide is recycled, the addition of fresh carbon dioxide can be dispensed with or at least significantly reduced.
  • carbon dioxide is produced as exhaust gas, which is usually released into the environment in state-of-the-art processes.
  • the process described here can have clear advantages in ecological aspects.
  • the process can be carried out with reduced resources and more cost-effectively. There are therefore particular advantages over solutions from the prior art.
  • Conventional processes for the thermal recycling of Li-ion batteries generate CO2 and emit the climate-damaging greenhouse gas into the environment, which runs counter to the attempt to reduce CO2 emissions from industrial processes.
  • the carbon dioxide is produced in the second thermal treatment step through the appropriate temperature control of the thermal pretreatment according to process step i) and the pyrolysis according to process step ii). This enables the resulting carbon dioxide to be generated and used in a targeted manner.
  • emissions reduction is thus permitted by circulating the CO2 and also high lithium yields without further additives, such as carbonating agents, which are necessary in the conventional process.
  • additional additives such as pH adjusting agents, for further hydrometallurgical treatment.
  • an increased amount of leaching agents such as HCl and H2SO4, pH adjusting agents such as NaOH or KOH, or oxidizing agents such as H2O2 are required because the water and CO2 based process means pre-separation of lithium and graphite. This achieves a mass reduction for hydrometallurgy, which can be avoided according to the invention.
  • the process for example before process step iv), comprises the further process step of flotation.
  • the method includes flotation to obtain the anode material.
  • the flotation preferably takes place after process step iii) and before process step iv).
  • process step v) takes place in such a way that recycled carbon dioxide is at least partially used in the flotation.
  • Flotation in a manner known per se, is to be understood as a physical-chemical separation process for fine-grained solids due to the different surface wettability of the particles.
  • the process takes place in a liquid, such as in particular water, and furthermore with the supply of gas, such as air.
  • anode material in particular graphite
  • graphite is usually used as anode material in energy storage devices and is also a valuable raw material that is classified as critical by the EU.
  • the anode material preferably comprises graphite.
  • the graphite offers a further significant advantage over prior art processes, according to which CO2 is produced by burning graphite and converting it to CO2/CO. According to the invention, however, it can be prevented that the loss of a critical raw material occurs with additional CO2 generation.
  • the graphite is inert.
  • the flotation process according to this embodiment can particularly preferably be carried out using carbon dioxide, since carbon dioxide is generated in-situ in the process, does not disrupt the process, and is also advantageously suitable for the formation of bubbles or foam.
  • the carbon dioxide recycled in process step v) is purified before being recycled, in particular into at least one process step of process steps ii) and/or iii) and/or into the flotation.
  • foreign substances that are in the gas stream can be removed. This can be achieved, for example, by a filter unit, through which it is possible to remove entrained solids from the gas stream. Additionally or alternatively, it is possible to also remove gaseous impurities from the gas stream by using gas separation processes known per se.
  • This step enables process step ii) to be carried out particularly efficiently, since no foreign substances or waste materials or, in principle, impurities are reintroduced into the product stream to be treated.
  • the product leaving process step ii) can therefore be improved in terms of the presence of undesirable foreign substances, which enables improved purification of the lithium obtained.
  • carbon dioxide is supplied as fresh gas to process step ii) at least temporarily.
  • This configuration can take into account the fact that the recycled carbon dioxide may not be sufficient to form the atmosphere in process step ii). Accordingly, new or non-recycled carbon dioxide can also be fed to process step ii). Adding fresh gas can be particularly advantageous when starting up the process.
  • the origin of the CO 2 fresh gas is not limited.
  • the CO 2 comes from a so-called CC process, which can also be referred to as carbon capture (in German: CO 2 separation), and the separation of carbon dioxide, in particular from combustion exhaust gases, and its subsequent use in other processes describes chemical processes.
  • This design can further improve the ecological aspects and thereby the sustainability of the process described here.
  • process step ii) is carried out in a continuously operated moving bed reactor. It has been shown that, particularly in this embodiment, effective carbonation of the lithium species can be permitted by circulating the material. This makes it possible to effectively wash out the lithium carbonate in further steps and thus to recover the lithium particularly effectively and cleanly.
  • process is not limited to a continuously operated moving bed reactor.
  • batch processes or other reactors are also possible in order to carry out the pyrolysis according to process step ii).
  • process step ii) is carried out at temperatures in a range from greater than or equal to 300 ° C to less than or equal to 800 ° C.
  • Process step ii) can preferably be carried out at temperatures in a range from greater than or equal to 350 ° C to less than or equal to 560 ° C, for example from greater than or equal to 400 ° C to less than or equal to 560 ° C.
  • the process step can be carried out in an energy-saving manner, particularly in this temperature range. In addition, however, it can be ensured that effective thermal carbonation takes place, so that It can be ensured that a large amount of lithium compounds are carbonated and react to form lithium carbonate.
  • the exhaust gas stream i.e. in particular the discharged and recirculated carbon dioxide stream
  • the waste heat from the carbon dioxide stream leaving the pyrolysis can be used to control the temperature of other processes, such as leaching the lithium carbonate or for hydrometallurgical processes.
  • the hot carbon dioxide can pass through a heat exchanger or be introduced directly into a process.
  • the exhaust gas can be recycled into the thermal pretreatment to set a suitable process atmosphere for the targeted phase transformations within the cathode material, which is particularly advantageous for subsequent treatments.
  • a mechanical processing of the product obtained in process step ii) is carried out between process steps ii) and iii).
  • This processing step can in particular serve to further concentrate the lithium-containing material in order to further improve the processing of the lithium.
  • this processing step serves, for example, to separate aluminum and copper foils as well as housing parts from the active mass if they are still present. This can be done, for example, using heavy sieve loading or impact mills.
  • This process step can be carried out in a manner understandable to those skilled in the art depending on the substances actually still present or their quantity.
  • no solid carbon is added in the process for thermal pretreatment and/or pyrolysis.
  • no coal, activated carbon, anthracite or the like is preferably added for thermal pretreatment and/or pyrolysis.
  • the subject of the present invention is also the use of a method as described above for processing a lithium-containing energy storage device.
  • the present invention relates to the use of a method as described above for the recovery of lithium and/or anode material from lithium-containing energy storage devices.
  • the method according to the invention preferably represents a method for recovering lithium and/or anode material from lithium-containing energy storage devices.
  • the defined use allows the resulting CO2 to be made usable and converted into a product through targeted recycling.
  • This has the advantages of a thermal Pretreatment without undesirable side effects.
  • the use of CO2 generated in the process as a usable resource for both lithium and graphite through an innovative recycling process makes this possible in a very advantageous way. Compared to state-of-the-art solutions, good ecological behavior is combined with comparatively low costs and a possible high purity of the lithium recovered. The process is therefore cost-effective and ecologically improved and enables economical lithium and graphite recovery.
  • Fig. 1 is a schematic flow diagram of an exemplary embodiment of a method according to the present invention.
  • Figure 1 shows schematically a flow diagram of a method of the present invention. Such a process is used to process lithium-containing energy storage devices and to recover the raw materials built into them, in particular the recovery of lithium.
  • an optional pretreatment 12 of the lithium-containing energy storage takes place.
  • This pretreatment 12 can be thermal, mechanical and/or electrical, for example, and can be used in particular to discharge or deactivate the energy storage device.
  • components of the energy storage can be removed 14.
  • the discharge 14 makes it possible, for example, to remove plastic components, metal components or even electrical components, without being limited to this, and thus to separate them from the lithium-containing product stream 16 to be further treated.
  • the pretreatment 12 preferably comprises at least one of the following process steps:
  • pyrolysis 18 of the continued product stream 16 or of the optionally pretreated energy storage, for example at temperatures in a range from 300 ° C to 800 ° C and / or in a moving bed reactor.
  • the pyrolysis 18 takes place under a carbon dioxide atmosphere and thus under reducing conditions, and with at least partial carbonation of the lithium contained.
  • materials contained in the product stream such as in particular active material and binder components, decompose, so that carbon dioxide is created or released during pyrolysis.
  • This processing step can in particular serve to further concentrate the lithium-containing product stream 16 in order to further improve the processing of the lithium.
  • this processing step serves, for example, to separate aluminum and copper foils and housing parts from the active mass or from the lithium-containing product stream 16 by means of a discharge 22, insofar as they are still present.
  • lithium is separated off in a separation step through a separation 24.
  • This can be done in particular by leaching the product obtained in the steps described above.
  • neutral leaching can take place in an aqueous solution by adding water to the product to be treated.
  • an aqueous solution with lithium can be removed in the form of lithium carbonate, which has formed as a water-soluble product in the pyrolysis, through a discharge 26.
  • a gas such as in particular carbon dioxide
  • a flotation container or the liquid contained therein with the lithium-containing product stream 16 whereby the graphite separates and can be removed from the lithium-containing product stream 16 by a discharge 30.
  • a hydrometallurgical processing 32 of the lithium-containing product stream 16 takes place, in particular with further carbonation of the lithium contained and with the separation of lithium in a further separation step through the discharge 34.
  • other components in particular metals, can be removed by pH change processes and/or by extraction processes be expelled.
  • Figure 1 further shows that carbon dioxide released during pyrolysis 18 is circulated in a circuit 36 and fed into at least one of the process steps of pyrolysis 18 and separation 24. Furthermore, the carbon dioxide can be fed to the flotation process 28. In principle, it may be preferred that the returned, i.e. supplied, carbon dioxide is purified before being recycled, i.e. supplied.
  • the circulation system 36 can already be sufficient to create a suitable atmosphere during the pyrolysis 18. However, it may be necessary for carbon dioxide to be supplied at least temporarily as fresh gas to the pyrolysis 18 through a feed 38. Additionally or alternatively, protective gas can be used Pyrolysis 18 are supplied, which can also be circulated and optionally purified.
  • a method is described, which also represents a method for lithium and anode material recovery from lithium-containing energy storage devices, the anode material comprising graphite.
  • Production scrap, cells, modules and optionally shredded material can be used as lithium-containing energy storage, with production scrap and modules being dismantled down to the cell level in this example.
  • a pretreatment 12 of the lithium-containing energy storage takes place.
  • This pretreatment 12 includes a thermal pretreatment of the energy storage device, which has been dismantled down to the cell level, at no more than 350 ° C to decompose the conductive salt and to volatilize solvent, the solvent being condensed for recovery, and comminution of the thermally pretreated lithium-containing energy storage device, so that in During the subsequent pyrolysis, shredded material is used as lithium-containing energy storage.
  • the discharge 14 makes it possible, for example, to remove plastic components, metal components or even electrical components and thus to separate them from the lithium-containing product stream 16 to be further treated.
  • a continuously operated pyrolysis 18 of the continued product stream 16 or the pretreated energy storage then takes place, for example at temperatures in a range from 500 ° C to 800 ° C in a moving bed reactor.
  • the pyrolysis 18 takes place under a carbon dioxide atmosphere that suppresses oxidation reactions and contains a protective gas selected from argon and nitrogen, and with at least partial carbonation of the lithium contained.
  • materials contained in the product stream such as in particular active material and binder components, decompose, so that carbon dioxide is created or released during pyrolysis.
  • This processing step serves in particular to further concentrate the lithium-containing product stream 16 in order to further improve the processing of the lithium.
  • this processing step is used, for example, to process aluminum and copper foils as well as housing parts Separate discharge 22 from the active mass or from the lithium-containing product stream 16, insofar as they are still present.
  • lithium is separated off in a separation step through a separation 24. This is done by leaching the product obtained in the steps described previously. In particular, neutral leaching takes place in an aqueous solution by adding water to the product to be treated. This means that an aqueous solution with lithium can be removed in the form of lithium fluoride and lithium carbonate (removal 26), which were formed as water-soluble products in the pyrolysis.
  • a hydrometallurgical processing 32 of the lithium-containing product stream 16 takes place with further carbonation of the lithium contained and removal of lithium in a further separation step by the discharge 34.
  • other components in particular metals, can be discharged by pH change processes and/or by extraction processes become.
  • carbon dioxide released during pyrolysis 18 can optionally be circulated in a circuit 36 and fed into at least one of the process steps of pyrolysis 18, separation 24 and flotation process 28.
  • the returned, i.e. supplied, carbon dioxide can be purified before being returned, i.e. supplied.

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Abstract

La présente invention concerne un procédé de reconditionnement d'accumulateurs d'énergie contenant du lithium, le procédé comprenant au moins les étapes suivantes : i) le prétraitement éventuel de l'accumulateur d'énergie contenant du lithium, le prétraitement comprenant au moins : un prétraitement thermique, et/ou mécanique et/ou électrique ; ii) la pyrolyse de l'accumulateur d'énergie contenant du lithium éventuellement prétraité, avec la libération de dioxyde de carbone, et avec au moins une carbonatation partielle, sous une atmosphère de dioxyde de carbone, du lithium contenu ; iii) la séparation du lithium à une étape de séparation ; et iv) le reconditionnement hydrométallurgique du mélange obtenu à l'étape iii), avec une carbonatation supplémentaire du lithium contenu et avec la séparation du lithium à une autre étape de séparation, v) le dioxyde de carbone libéré à l'étape ii) étant renvoyé à au moins l'une des étapes ii) et iii).
PCT/EP2023/073322 2022-08-30 2023-08-25 Procédé de reconditionnement d'accumulateurs d'énergie contenant du lithium WO2024046889A1 (fr)

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