Method for recycling lithium batteries

Abstract

The present invention relates to a method for recycling lithium batteries, the method comprising the steps of: (a) using concentrated sulfuric acid (12) to decompose pulverized material (10) containing pulverized components of the lithium battery electrode at a decomposition temperature (TA) of at least 100°C, particularly at least 140°C, thereby generating waste gas (14) and decomposed material (16); (b) discharging the waste gas (14); and (c) wet chemically extracting at least one metallic component of the decomposed material (16).

Description

[0001] This application is a divisional application of patent application No. 201980010559.3, filed on January 29, 2019, entitled "Method for Recycling Lithium Batteries". Patent application No. 201980010559.3 is the Chinese national phase application of PCT application No. PCT / EP2019 / 052122. Technical Field

[0002] This invention relates to a method for recycling lithium batteries. According to a second aspect, this invention relates to a recycling apparatus for processing lithium batteries. Background Technology

[0003] Lithium-ion batteries are a type of battery that stores electrical energy through a lithium-based electrochemical reaction. They have a wide range of applications. However, the recycling of lithium-ion batteries remains problematic. It is not yet possible to recover the graphite contained in the electrodes to a quality that can be reused in the production of lithium-ion batteries. Lithium recycling also presents challenges. Furthermore, cobalt, nickel, and manganese, which may be present in lithium-ion batteries, can typically only be recovered by weight, making their use in new lithium-ion batteries economically impractical. When considered holistically, the material recovery efficiency of known recycling methods, at the battery cell level, is less than 50% by weight.

[0004] US 2004 / 0028 585 A1 describes a method for recovering vanadium from lithium metal polymer batteries. According to one variation, this involves mixing pulverized material with 30% dilute sulfuric acid. Vanadium is then obtained from the resulting aqueous solution in the form of vanadium pentoxide. Therefore, this method is only feasible when the vanadium content in the pulverized material is sufficiently high. However, this is not the case, for example, in commonly used lithium-ion batteries. Furthermore, other metallic components, such as cobalt, nickel, and manganese, can only be extracted with great difficulty. The use of concentrated sulfuric acid is not recommended for various reasons, including safety concerns.

[0005] US 2017 / 0077564 A1 describes a method for recycling lithium-ion batteries in which pulverized material is leached with an aqueous solution of dilute sulfuric acid and hydrogen peroxide. A drawback of this method is that achieving the highest recovery rate is extremely complex.

[0006] An article titled "Acid leaching of mixed spent Li-ion batteries" published by Nayl et al. in the Arabian Journal of Chemistry, 2017, 10, pp. 3632-3639, also describes a lithium battery leaching method using dilute sulfuric acid and hydrogen peroxide. It was found that the degree of leaching initially increased with increasing sulfuric acid concentration, then decreased from 3 M. The highest concentration examined was 4 M. Summary of the Invention

[0007] The present invention aims to improve the recycling rate of lithium batteries.

[0008] The present invention addresses this problem by a method for recycling lithium batteries, comprising the following steps: (a) digesting pulverized material (10) containing pulverized components of lithium battery electrodes using concentrated sulfuric acid at a digestion temperature of at least 100°C, preferably at least 120°C, particularly preferably at least 140°C, thereby generating waste gas and digested material; (b) discharging the waste gas; and (c) wet chemically extracting at least one metallic component from the digested material, particularly at least one metallic component selected from the list containing cobalt, lithium, manganese, nickel and titanium (preferably two, three, four or more metallic components).

[0009] According to a second aspect, the present invention addresses this problem by a recycling apparatus for processing lithium batteries, particularly used lithium batteries, comprising: (a) a reactor for digesting pulverized material containing pulverized components of lithium battery electrodes using concentrated sulfuric acid at a digestion temperature of at least 50°C; (b) a sulfuric acid supply device for adding sulfuric acid to the pulverized material; and (c) an emission device arranged to discharge waste gas from the reactor. The emission device is particularly designed to be resistant to hydrogen fluoride. In other words, hydrogen fluoride cannot escape into the surrounding environment.

[0010] The advantage of this invention is that any fluorides that may be present in the pulverized material can be completely removed during the digestion of the material with sulfuric acid, which is preferably concentrated. Fluorine compounds can form hydrogen fluoride, which is an extremely challenging problem from an occupational safety perspective. Hydrogen fluoride is also highly corrosive. By digesting the pulverized material with sulfuric acid, fluorides can be removed from the pulverized material, allowing subsequent steps in the process to be performed with fewer safety precautions and less material abrasion. Some separation methods (e.g., membrane separation methods, bipolar membrane electrodialysis) cannot be carried out in fluids with high fluoride levels; however, this preparation makes this possible. Furthermore, no impurities caused by fluorine substances occur, thus other components of the pulverized material can generally be recovered with high purity.

[0011] Another advantage is that battery graphite can often be recycled with high purity, so it can be used to manufacture new electrodes.

[0012] Equally feasible is a method that typically involves recovering lithium to a sufficiently high purity suitable for producing new lithium-ion batteries. Cobalt, nickel, manganese, and / or titanium can also be recovered to high purity, making them suitable for reuse in batteries, as long as they are present in the pulverized material.

[0013] Of particular advantage is that, in most cases, a recycling efficiency of more than 50% by weight of the battery cell can be achieved.

[0014] It should be noted that specific advantages may arise, but it is not always necessary to do so.

[0015] Known methods focus on the recovery of cobalt and nickel, as they represent the highest material value of used lithium batteries. It is generally accepted that other components from used lithium batteries, such as graphite and / or lithium, cannot be recycled. Recovering fluorides is also not a priority for known methods due to their low resale value.

[0016] Of particular advantage is that, in most cases, the method according to the invention can be designed to require less energy compared to pyrometallurgical methods. Specifically, according to a preferred embodiment, the method does not include a pyrometallurgical step.

[0017] As known from DE 10 2015 207 843 A1, it is advantageous to dry the battery at a low temperature after pulverization to prevent the formation of fluorinated organic compounds. During this drying process, organic carbonates present in the electrolyte are removed. Therefore, fluorinated compounds remain in the pulverized material. According to a preferred embodiment, the digestion is carried out on a pulverized material containing at least one fluorinated compound.

[0018] Within the scope of this specification, the method for recycling lithium batteries should be specifically understood as a method for recovering the metallic components of lithium batteries. In this sense, the method according to the invention is also a method for extracting metallic components from lithium batteries. The metallic components are, for example, lithium and / or transition metals, especially metals of Groups VI, VII, and VIII. Transition metals are preferably manganese and / or cobalt and / or nickel. Recovery of copper and / or titanium is also feasible.

[0019] Within the scope of this specification, a lithium battery should be specifically understood as a rechargeable battery whose electrochemical reaction involves lithium and / or lithium ions and / or lithium compounds. The battery comprises at least a primary cell.

[0020] Preferably, the lithium battery is at least partially a lithium-ion battery. Particularly preferred is that the pulverized material contains at least 40%, and particularly 60%, of lithium-ion batteries by weight. Lithium-ion batteries comprise a fluoride-containing liquid electrolyte: this electrolyte makes the recycling of the lithium battery very difficult.

[0021] The fluoride content in the pulverized material is preferably less than 7% by weight, and particularly less than 5% by weight.

[0022] The fluoride content in the pulverized material is preferably at least 0.5% by weight, and particularly at least 1% by weight.

[0023] Recycling equipment should be understood in particular as a device that separates one, two, three or more metal components in a lithium battery from the other components of the lithium battery, so that it can be further processed.

[0024] When temperatures are specified in the following description, they always refer to the average temperature within the corresponding object. For example, digestion at a digestion temperature of at least 50°C should be specifically understood to mean that the average temperature of the pulverized material mixed with sulfuric acid is 50°C. It is not important that there may be localized higher or lower temperatures. If no temperature is explicitly mentioned, the corresponding steps in the process are preferably carried out at room temperature and ambient atmospheric pressure.

[0025] Digestion should be understood in particular as the absence of dilute sulfuric acid. Specifically, at least at some point during the reaction, the concentration of sulfuric acid is above 90%, particularly 95%, and especially preferably 98%.

[0026] Specifically, digestion is carried out in such a manner that fluorides are removed in the form of hydrogen fluoride. In particular, digestion is performed such that the fluorine components in the pulverized material migrate into the exhaust gas in the form of hydrogen fluoride. In other words, very little water is present in the mixture of pulverized material and sulfuric acid, such that the concentration of water-soluble fluorides in each kilogram of digested material is less than 100 milligrams, and especially less than 10 milligrams per kilogram of digested material.

[0027] The characteristic of digesting pulverized materials with concentrated sulfuric acid should be understood in particular as the fact that the concentration of sulfuric acid is very high during the time intervals of the method, thereby achieving the aforementioned concentration of water-soluble fluoride per kilogram of digested material. Preferably, the concentration of sulfuric acid is at least 95% during the execution of the method, more preferably at least 98%. Unlike the case when using non-concentrated sulfuric acid, the use of concentrated sulfuric acid means that the digested material contains almost no fluoride.

[0028] Specifically, digestion is not leaching, because leaching is always carried out with aqueous fluids.

[0029] In particular, the digestion material is a solid. Unlike methods that do not use concentrated sulfuric acid, the reaction products, especially metal sulfates, are not soluble in water and are retained in solid form.

[0030] The term "crushed material" should be understood in particular as referring to material produced by the crushing of a lithium battery or at least one component of a lithium battery, especially an electrode, and, where applicable, by post-processing (e.g., drying). In this manner, several separation steps can be performed after crushing to separate the crushed metal foil, plastic foil, or battery casing and module assemblies. It is feasible that the crushed material contains up to 10% by weight, preferably up to 5% by weight, of plastic and / or metallic impurities. The crushed material may contain powdered components from the electrodes of the lithium battery. In a more general form, non-crushed materials, particularly electrode materials, can be used instead of the crushed material. However, it is advantageous to crush such electrode materials.

[0031] Specifically, the pulverized material can be material that has not undergone any pyrometallurgical treatment, particularly calcined and burned material. However, it is also possible and included in this invention that the pulverized material has not undergone any pyrometallurgical treatment.

[0032] The discharge of exhaust gases should be understood in particular as the exhaust gases being directed, at least to a large extent, away from the dissipation point. The exhaust gases may be extracted. Exhaust gases typically contain fluorinated compounds, especially hydrogen fluoride. It is possible, but not necessary, to remove hydrogen fluoride from the exhaust gases, particularly by precipitation, preferably using calcium compounds. The exhaust gases may also be added to chemical processes.

[0033] Wet chemical extraction should be specifically understood as the addition of a substance that is liquid at 1013 hPa and at room temperature, or is liquid in the added state, to a digestion material or a substance derived from a digestion material, resulting in the separation of at least one substance containing a metal or being a metal in itself.

[0034] The sulfuric acid is preferably at least 90%, particularly preferably at least 95%. However, it is possible to add low concentrations of sulfuric acid to the pulverized material. In this case, the digestion temperature is preferably the temperature required to evaporate enough water from the sulfuric acid to ensure a concentration of at least 90%, and especially at least 95%. The percentages referred to are usually percentages by weight.

[0035] The digestion of pulverized materials preferably includes the step of mixing the pulverized materials with sulfuric acid. Mixing may include spraying with sulfuric acid and / or forced mixing, such as extrusion, kneading, or stirring.

[0036] The digestion temperature is preferably below the boiling point of sulfuric acid to prevent its evaporation. Therefore, the digestion temperature is preferably below 335°C. Preferably, the digestion temperature is below the digestion temperature of the binder, by which the active material is bound to its carrier. Alternatively, the digestion temperature can be higher than the binder's digestion temperature. This prevents the binder from contaminating the graphite. However, it should be noted that the pulverized material may, but does not necessarily, contain a suitable binder. Temperatures between 150°C and 250°C are particularly advantageous.

[0037] Digestion can be performed under a protective gas (such as nitrogen or argon), as in other steps of this method, to prevent graphite oxidation. Other steps in this method can also, but do not necessarily, be performed under a protective gas.

[0038] Like the other steps in this method, the digestion can be performed discontinuously or continuously.

[0039] According to a preferred embodiment, the digestion material contains up to 15% water, particularly less than 10%, preferably less than 5%. If almost no water or no water is present, the fluoride is removed in the form of hydrogen fluoride, so there is almost no or no fluoride residue.

[0040] The process is preferably carried out until the concentration of hydrogen fluoride in the exhaust gas is below 0.83 mg / m³. Preferably, the hydrogen fluoride concentration is below a traceability threshold. The traceability threshold specifically refers to infrared spectroscopy measurements. This ensures that no significant amounts of hydrogen fluoride are released in subsequent steps of the method.

[0041] Alternatively or otherwise, digestion is performed until the fluoride concentration c of the water-soluble fluoride in the digestion material is reached. F Less than 100 mg per kilogram of digested material, preferably less than 10 mg / kg, and particularly preferably less than the traceability threshold.

[0042] Preferably, sulfuric acid is added to the pulverized material at least stoichiometrically, but more preferably in excess stoichiometrically. This should be understood in particular as adding sufficient sulfuric acid to make it possible to extract all non-precious metals and copper from the pulverized material, and, according to preferred embodiments, to extract them in subsequent steps of the method. Specifically, sufficient sulfuric acid is added to ensure that all non-precious metals and copper in the pulverized material dissolve at least 99% by weight. It should be noted that even with an excess stoichiometric addition of sulfuric acid, metal residues that have not reacted with the sulfuric acid may remain due to the limited nature of the reaction rate and the regulation of chemical equilibrium.

[0043] Preferably, concentrated sulfuric acid is used at a weight ratio of up to 40:1, particularly up to 20:1, and preferably up to 10:1, relative to the weight of the pulverized material. In other words, up to 40 kg of concentrated sulfuric acid is added per kilogram of pulverized material.

[0044] For example, it is beneficial to add at least 1.8 grams of H2SO4 per gram of cathode material, and particularly to add 1.8 grams of H2SO4 per gram of electrode active material. Specifically, the cathode material is LiMO2, where M represents a transition metal or aluminum. The cathode is the positively charged electrode during discharge.

[0045] The method preferably includes the step of separating hydrogen fluoride from the exhaust gas, and in particular, precipitating hydrogen fluoride from the exhaust gas. This is achieved, for example, by a calcium compound, resulting in the formation of calcium fluoride.

[0046] The method preferably includes the steps of leaching and digesting the material and separating the graphite, thereby producing a feed fluid. Advantageously, the method includes the step of separating powdered components from metal foils and metal and plastic sheets, thereby obtaining a separated powder made of electrode active material.

[0047] Leaching is preferably carried out using aqueous fluids, especially water.

[0048] The weight ratio of the digesting material to the aqueous fluid is preferably 1:2 to 1:20. Leaching is carried out for at least 1 minute, and preferably for a maximum of 10 hours. Separation is preferably by filtration. However, it is also possible to centrifuge or separate the graphite in another manner. Digestion with sulfuric acid generally results in a low concentration of metals, especially metal ions, in the graphite, making it suitable for use as electrode graphite in the production of new lithium batteries or other batteries.

[0049] It is possible that the method includes a step of washing the separated graphite, which can be done, for example, with water or a dilute inorganic acid.

[0050] Preferably, the washing is thorough, resulting in a metal ion concentration of <10 mg / kg in the wash water. It has been demonstrated that in known methods, the crystal structure of graphite is severely damaged, rendering it unusable as electrode graphite. Because of this, according to a preferred embodiment of the method, no wet chemical or thermal oxidation occurs before the graphite is separated, thus the crystal structure of the graphite is minimally damaged, allowing it to be frequently reused in batteries.

[0051] During leaching, the pH value is preferably between -0.7 and 4. Leaching is preferably carried out at room temperature; however, this is not mandatory.

[0052] Preferably, the method includes the step of separating copper from the feed fluid, thereby producing a copper-free feed fluid. It is possible, but not mandatory, that the copper separation is a wet chemical process that occurs immediately after leaching. In particular, it is also possible to separate other metals prior to copper separation. Specifically, this refers to selective copper separation. The temperature during copper separation is preferably between 0°C and 100°C. The separation is preferably carried out within 1 minute to 720 minutes.

[0053] Separation can be achieved through cementation. In the case of cementation, copper ions undergo an electrochemical reaction, resulting in the formation of elemental copper. For example, cementation can be performed using an iron substrate.

[0054] Alternatively, separation may involve precipitation. For example, copper can precipitate as copper sulfide. For this purpose, the feed fluid is supplied to a precipitant, such as a sulfur-containing substance. This could refer to sodium hydrogen sulfide. In this case, copper sulfide precipitates, particularly CuS. It is advantageous to add an excess of the precipitant in stoichiometric amounts, so that the concentration of copper ions in the feed fluid for copper removal is preferably less than 10 mg / L, particularly preferably less than 1 mg / L.

[0055] This method preferably includes the steps of removing iron oxide ions and precipitating iron. Specifically, the Fe in the copper-removing feed fluid... 2+ Ions are oxidized to form Fe 3+ Ions. This can be achieved using oxidizing agents (such as oxygen compounds). Oxygen compounds can be, for example, hydrogen peroxide or ozone.

[0056] Iron precipitation preferably occurs in the form of hydroxides. The precipitation produces a pure fluid.

[0057] It is particularly advantageous if aluminum is preferably precipitated as a hydroxide. It is also beneficial if, if present, titanium is precipitated, preferably as titanium oxide.

[0058] Precipitation of iron and / or aluminum and / or titanium preferably occurs due to the addition of NaOH, Na2CO3, KOH, MgO or ammonium hydroxide.

[0059] It should be noted that the term "pure fluid" should only indicate that metals considered impurities, such as iron, and, where applicable, copper, aluminum, and titanium, have been removed. Specifically, the term "pure fluid" is not intended to give any indication of the concentration of other substances.

[0060] The characteristic of oxygen compounds being used in oxidation processes should be understood as meaning that oxygen changes its oxidation number during a redox reaction. Alternatively, a compound can be used as an oxidizing agent; for example, the compound contains oxygen but its oxidation number remains unchanged during a redox reaction.

[0061] Oxidation is preferably carried out until the electrochemical potential relative to a conventional hydrogen electrode is between 0.8 and 1.4 volts. Within this voltage range, modified Fe will occur.2+ ⇌Fe 3+ + e - .

[0062] Preferably, the pH value during oxidation is at most 8.7. During precipitation, the pH value is preferably at least 4.3, particularly preferably 4.8. In particular, the pH value during precipitation is at most 8.7, preferably at most 7.8. As a result, iron and / or aluminum and / or titanium precipitate in large quantities.

[0063] This method preferably involves solvent extraction of cobalt. Extraction from a pure fluid is preferred. Particularly advantageous for this is the use of a cobalt complexing agent, such as a complexing agent dissolved in a lipophilic fluid. The lipophilic fluid can be, for example, mineral oil, such as kerosene. Another possibility is the use of hypophosphonic acid, such as Cyanex 272 (bis(2,4,4-trimethylpentyl)hypophosphonic acid).

[0064] The method preferably includes a subsequent step of solvent extraction of nickel. Preferably, this is done using a nickel complexing agent. Extraction of the solvent from a pure fluid is advantageous. The complexing agent is preferably dissolved in a lipophilic fluid, such as a mineral oil similar to kerosene.

[0065] It is feasible to extract cobalt and nickel from pure fluids during the combined extraction process, thus obtaining a fluid rich in cobalt and nickel.

[0066] Preferably, in the subsequent extraction step, manganese is removed from the fluid, particularly by solvent extraction, preferably by a manganese complexing agent.

[0067] For example, Cyanex 301 (bis(2,4,4-trimethylpentyl)dithiophosphonic acid) is well-suited for extracting nickel or cobalt, where Cyanex can be pre-dissolved in kerosene for use. Nickel can be further extracted from the charged organic phase, for example, using hydrochloric acid or sulfuric acid, and then crystallized as nickel chloride or nickel sulfate. Cobalt can also be further extracted from the loaded organic phase using, for example, hydrochloric acid and / or sulfuric acid, and then crystallized as cobalt chloride or cobalt sulfate. Additionally, manganese can be further extracted from the charged organic phase using hydrochloric acid and / or sulfuric acid, and then crystallized as manganese chloride or manganese sulfate. Alternatively, manganese can be precipitated, for example, as a carbonate.

[0068] Removing cobalt, nickel, and / or manganese produces the target fluid. Preferably, lithium precipitates from the target fluid. This can occur, for example, by adding a phosphate (e.g., sodium phosphate) or a carbonate (e.g., sodium carbonate). Lithium precipitation preferably occurs at a pH of 7 to 14.

[0069] If the pure fluid contains neither cobalt nor nickel or manganese, it is preferable to precipitate lithium from the pure fluid (28). This is the case, for example, if only lithium iron phosphate batteries are used to produce pulverized materials.

[0070] Preferably, the pulverized material comprises powdered electrode material from a lithium-ion battery. The pulverized electrode foil, separator foil, other foils, battery casing material, and battery module peripheral components are separated from the pulverized lithium-ion battery to obtain powdered electrode active material.

[0071] The pulverized material is preferably obtained by pulverizing a battery and then deactivating the resulting pulverized raw material by drying. Pulverization is particularly advantageous if it is carried out in an inert gas atmosphere and / or under vacuum. If pulverization occurs under vacuum, the pressure is preferably up to 300 hPa. Preferably, the temperature is up to 100°C, more preferably up to 80°C. This prevents the formation of fluorinated organic compounds. Fluorides remain in the pulverized material and are removed by digestion using sulfuric acid, as described above.

[0072] According to a preferred embodiment, after deactivation, the pulverized metal current collector foil, the insulating foil of the battery casing assembly, and the module assembly are separated to obtain pulverized material.

[0073] Pre-discharging and / or obtaining the battery is preferably achieved by disassembling the battery system or battery module.

[0074] In the case of the recycling equipment according to the invention, the reactor is preferably a rotary kiln or a heated forced mixer. This ensures thorough mixing of the sulfuric acid with the pulverized material. The reactor is characterized by, for example, a temperature control or regulator, by which the temperature of the mixture of pulverized material and sulfuric acid is raised to and maintained at the digestion temperature. Digestion may also occur discontinuously, for example in a chamber furnace.

[0075] According to a preferred embodiment, the recycling equipment includes a leaching device for leaching the digested material in an aqueous medium.

[0076] The recovery equipment preferably includes a fluoride separator for separating hydrogen fluoride. For example, hydrogen fluoride can be precipitated. However, it is also possible that the hydrogen fluoride reacts with another substance, such as an organic substance.

[0077] It is advantageous if the recycling equipment is designed to be mobile. In other words, the recycling equipment can be moved without having to be disassembled. The recycling equipment is preferably housed in a 20-foot or 40-foot container.

[0078] The transport of pulverized material typically involves risks due to its flammable content and fluorine compounds. Therefore, there is a risk (possibly a small, acceptable risk) of fire caused by the release of hydrogen fluoride. Consequently, it is feasible to locally separate the electrolyte, battery components, electrode foil, and electrode powder. Therefore, it is advantageous, as described in DE 10 2015 207 843 A1, that the recycling equipment includes battery processing equipment for pulverizing lithium batteries. Then, for the reactor, a sulfuric acid supply device and a discharge device, as well as any other devices specified in the claims, may, but are not required, be designed to be mobile and preferably arranged together within a 20-foot or 40-foot container.

[0079] The recycling equipment preferably includes a graphite recycling unit having a graphite separation device, particularly a filter, for separating graphite, and is arranged downstream of the reactor in the direction of material flow.

[0080] According to a preferred embodiment, the graphite recovery apparatus includes a rinsing device for washing away the leaching solution adhering to the graphite. This rinsing device is preferably designed to rinse the leaching solution with an aqueous fluid.

[0081] The recovery equipment preferably includes a fluoride detector for detecting fluorine compounds, especially hydrogen fluoride. The fluoride detector is preferably a hydrogen fluoride analyzer for measuring the concentration of hydrogen fluoride in exhaust gas.

[0082] According to a preferred embodiment, the recovery device has a control unit connected to a fluoride detector and designed to automatically control the reactor, such that it maintains the digestion temperature until the concentration of fluorides, particularly hydrogen fluoride, in the exhaust gas drops below a predetermined threshold.

[0083] According to a preferred embodiment, the recovery device has a precipitate separator for separating, in particular filtering, the precipitated Cu or Cu compounds.

[0084] Advantageously, the recovery equipment has a solvent extraction device for extracting cobalt, manganese and / or nickel, which is arranged behind the graphite recovery device in the direction of material flow.

[0085] The recovery equipment preferably also includes an Fe / Al / Ti precipitate separator for separating, and in particular filtering, the precipitated iron and / or aluminum and / or titanium compounds. The Fe / Al / Ti precipitate separator is preferably arranged behind the rotary kiln in the direction of material flow, and, if available, before the solvent extraction unit.

[0086] Preferably, the maximum temperature subjected to the pulverized or digested material is 1000°C, more preferably at most 700°C, and particularly less than 335°C. The pulverized material is preferably not subjected to a bursting treatment.

[0087] The recycling equipment according to the invention preferably has a pulverizing unit for pulverizing lithium batteries, thereby obtaining shredded material. The recycling equipment preferably also has a deactivation device for inactivating the shredded material. Advantageously, the deactivation device includes a drying device configured to dry the shredded material until the electrolyte content of the pulverized material is so low that an electrochemical reaction is impossible.

[0088] The recovery equipment preferably includes a vacuum device connected to the drying equipment to create a vacuum within the drying equipment.

[0089] It is feasible to design the vacuum device to generate a vacuum of at least 300 hPa. In other words, the vacuum device is designed to achieve a pressure of 300 hPa or less. To ensure low instrumentation complexity, the vacuum device is preferably configured to achieve a maximum possible pressure greater than 0.01 Pa, and more preferably greater than 1 Pa.

[0090] The recycling equipment preferably includes a cemented carbide separation device for separating cemented carbide from the pulverized material. The cemented carbide separation device should be specifically understood as a device for separating fragments of the peripheral components of the electrical contacts of battery systems, battery cells, and / or lithium batteries. For example, the cemented carbide separation device includes a magnetic separation device and / or a separator, particularly a cross-flow separator and / or a zigzag separator.

[0091] Alternatively or additionally, the recovery equipment preferably includes a light component separation device for separating light components, which may include, for example, separator foil and coating material. The light component separation device preferably has a zigzag separator and / or an air separator, wherein it is advantageous if the air in the light component separation device is conducted within a loop. This reduces environmental exposure to dust. The air separator may be an air jet screen.

[0092] It is advantageous if the recycling equipment has a separation device, particularly a sorting device, for separating the active material from the carrier, especially by air-jet screening and / or a second pulverizing stage, thereby producing fragments of the active material and carrier fragments. Specifically, the carrier fragments include aluminum and copper foil.

[0093] For recycling equipment, a filling device may be necessary, but is not required, for filling a transport container with pulverized material. This transport container allows the pulverized material to be transported over longer distances, if necessary, such as at least 1 km. The pulverized material can then be discharged from the transport container and fed into the reactor.

[0094] Alternatively, the recycling equipment may not have a filling device for filling transport containers with pulverized material. In this case, it is preferable to transport the pulverized material to the reactor via a continuous or discontinuous conveyor after pulverization and introduce it into the reactor. Attached Figure Description

[0095] The invention will be explained in more detail below with reference to the accompanying drawings, which are shown as follows:

[0096] Figure 1 This is a flowchart of the method according to the present invention, and

[0097] Figure 2 This is a schematic diagram of a recycling device according to the present invention.

[0098] Figure 3 This is a flowchart of a method for processing pulverized materials that do not contain cobalt, nickel, and manganese, according to the present invention.

[0099] Figure 4 This is a flowchart of a method for processing pulverized materials that do not contain cobalt and nickel but do contain manganese, and...

[0100] Figure 5 This is a flowchart of a method according to the present invention for pulverizing materials that do not contain manganese and nickel but contain cobalt.

[0101] Figure 6 This is a flowchart for processing pulverized materials that do not contain manganese but contain cobalt and nickel.

[0102] Figure 7 This is a schematic diagram of the crushing unit of the recycling device according to the present invention. Detailed Implementation

[0103] Figure 1 A flowchart of the method according to the invention is shown. First, a pulverized material is provided, for example, in the form of pulverized electrode active material. This can be achieved, for example, using the method described in DE 10 2015 207 843 A1. In particular, the battery can be pulverized first to obtain pulverized raw material. In a subsequent step, the pulverized raw material is deactivated by drying to obtain deactivated pulverized raw material.

[0104] Deactivation is preferably achieved through drying. Drying can be carried out, for example, in an inert gas atmosphere or under vacuum. A maximum pressure of 300 hPa and a maximum temperature of 80°C during drying are advantageous. This results in the pulverized material 10 no longer undergoing significant electrochemical reactions because the proportion of low-boiling-point substances in the electrolyte is too low.

[0105] According to a preferred embodiment, after deactivation, the electrode active material is separated from the pulverized raw material. Preferably, this includes a combination of mechanical stress, magnetic separation, non-ferrous metal separation, sieving, and density separation. Practically, an air-jet sieve is used, where sieving with a smaller sieve aperture size produces a purer sieved material.

[0106] The pulverized material 10 is mixed with sulfuric acid 12. Mixing can be achieved, for example, by stirring with a stirrer. However, mixing can also be a simple addition. This is particularly possible if the pulverized material 10 is in a reactor in the form of a rotary kiln. Alternatively, the pulverized material and sulfuric acid can be mixed in a reaction vessel, preferably made of steel. The resulting mixture of pulverized material is then added to the reactor, particularly a rotary kiln.

[0107] Sulfuric acid 12 is preferably at least 95%. The pulverized material 10 and sulfuric acid 12 are heated to the digestion temperature T. A For example, at least T A =140℃, especially at least 150℃. Within a range where the pH value can be determined, the pH value of a mixture of pulverized material and sulfuric acid is below 1.5. However, generally, the water content of the mixture is too low to determine the pH value.

[0108] The digestion process generates waste gas 14, which contains, in particular, hydrogen fluoride (HF). Digestion continues until the fluoride content (especially the hydrogen fluoride content) in the waste gas 14 falls below a predetermined threshold, for example, 0.83 mg per cubic meter in a discontinuous comparative test in a container when materials are added intermittently. This is checked using a fluoride detector 15 that continuously measures fluoride concentration.

[0109] If digestion is carried out during the loading process, digestion continues until the content of fluorine compounds, especially hydrogen fluoride, is below a predetermined threshold, such as 0.83 mg per cubic meter.

[0110] Alternatively or otherwise, digestion is carried out until the fluoride concentration c of water-soluble fluorides in the digestion material is reached. F The concentration of fluoride in the digested material is below 100 mg / kg, preferably below 10 mg / kg, and particularly preferably below the traceability threshold. In other words, the holding time of the pulverized material 10 and sulfuric acid 12 is selected so that the digested material has a fluoride concentration c of water-soluble fluoride not exceeding a specific value. F .

[0111] Additionally, a digestible material 16 is obtained, which can be well approximated as fluoride-free. Water 18 is added to the digestible material 16, thereby leaching it. Leaching may occur in the same container where the pulverized material was digested; however, this is not necessary. For example, the digestible material can be placed in a container that is preferably already filled with water. The leaching occurs at a pH of -0.7 to 4, and preferably without the active addition or release of heat.

[0112] After leaching, graphite 20 is separated using a graphite separation device 22. Currently, the graphite separation device 22 is a filter with a maximum pore size of 15 micrometers, preferably a maximum of 10 micrometers. A pore size of at least 0.5 micrometers is advantageous.

[0113] In subsequent steps of this method, graphite 20 can be washed, for example, with water, alcohol, organic solvents, or inorganic acids, to obtain electrode graphite. Electrode graphite is suitable for producing electrodes, particularly for lithium batteries. This generates a feedstock fluid 24.

[0114] Metallic copper (Cu) is obtained from the feed fluid 24, for example, by cementation. For this purpose, metallic iron is brought into contact with the feed fluid 24, causing the iron ions to dissolve and the copper to precipitate metallically.

[0115] Alternatively, copper is separated as copper sulfide. This can be achieved, for example, by adding sodium hydrosulfide (NaHS) via precipitation. The separation of copper results in a copper-free feed fluid 26. Its pH is between 0 and 4, for example, pH 1.

[0116] Then the Fe in the copper-removing raw material fluid 26 2+ Ion oxidation to form Fe 3+ Ions. In the current case, this is achieved by adding hydrogen peroxide (H₂O₂). However, different oxidants can also be used. Prior to oxidation, the pH of the copper-removing feed fluid is below 4.3. This step is preferably carried out without active heat supply or extraction.

[0117] In subsequent steps, iron, aluminum, and titanium (if applicable) precipitate as hydroxides. For this, the pH is increased to a value between 4.3 and 8.7. This can be achieved by adding sodium hydroxide and then separating (particularly by filtration or centrifugation) the resulting precipitate. In addition to the separated hydroxides, a pure fluid 28 is obtained. Solvent extraction is used to extract nickel and cobalt from the pure fluid. In the present case, this is achieved by dissolving Cyanex 301 in an organic solvent (typically kerosene).

[0118] Figure 1The diagram illustrates two nested solvent extraction steps. First, cobalt and nickel are extracted using Cyanex 301 dissolved in kerosene. Eluting is then performed using acids, particularly hydrochloric or sulfuric acid, to obtain a solution 30 containing nickel and cobalt. After further separation using Cyanex 272, they are crystallized separately.

[0119] If a metal is specifically named as commonly herein or in the specification (such as manganese), it generally refers to the metal in its basic form and the compounds contained therein; it usually also includes metal ions. Therefore, statements about the extraction of manganese, cobalt, and nickel also mean the removal of manganese, cobalt, and nickel ions, as well as any compounds, especially those containing manganese, cobalt, and nickel.

[0120] The extraction of cobalt and nickel produces a target fluid 32 containing manganese. The pH of the target fluid 32 can be between -0.7 and 10.5.

[0121] There are at least three alternatives available for further processing of the target fluid 32. According to the first alternative, manganese in the manganese-containing target fluid 32 can be removed by solvent extraction. For example, this can be achieved using D2EHPA dissolved in kerosene.

[0122] According to the second and third alternatives, manganese is removed by precipitation, which can occur, for example, by adding sodium hydroxide. According to the third alternative, precipitation can occur by adding sodium carbonate.

[0123] Manganese is removed to produce target fluid 34. The most important component of this fluid is lithium ions. Lithium is precipitated from target fluid 34. This is done, for example, using sodium carbonate. An advantageous temperature is at most 30 Kelvin below the boiling point of target fluid 34, and preferably above 50 Kelvin.

[0124] Lithium carbonate can be washed with water and / or ethanol at 50-100°C, preferably 80-100°C.

[0125] It is beneficial to perform a concentration step before the precipitation step, thereby increasing the lithium concentration. Alternatively, lithium can be precipitated as lithium phosphate; for this purpose, sodium phosphate can be added, for example.

[0126] Concentration can occur, for example, through reverse osmosis and / or evaporation.

[0127] Figure 2A schematic diagram of a recycling apparatus 36 for processing lithium batteries according to the present invention is shown, wherein the lithium batteries are in the form of pulverized material 10 generated from the lithium batteries. Alternatively, electrode materials that do not require pulverization can also be processed in the recycling apparatus. In the present case, the recycling apparatus 36 has a reactor 40 in the form of a rotary kiln, wherein the pulverized material 10 is digested using sulfuric acid 12. The pulverized material 10 and sulfuric acid 12 have been pre-mixed together in a mixer 42. The mixer 42 is advantageous but not necessary. The sulfuric acid 12 is added via a sulfuric acid supply device 43, which can, for example, refer to a metering device comprising a sulfuric acid container and a controlled valve. However, sulfuric acid 12 can also be poured in from a container.

[0128] The recovery device 36 has an exhaust pipe-like discharge device 44, which can be connected to a vacuum generator to draw the exhaust gas 14 out of the reactor 40. Alternatively, excess pressure in the reactor 40 can be used to force the exhaust gas 14 through the discharge device 44. The discharge device 44 may have a scrubber for flushing out hydrogen fluoride. For example, in this scrubber, the exhaust gas 14 is contacted with a calcium compound, such as an aqueous solution containing calcium ions, thereby flushing out the hydrogen fluoride from the exhaust gas 14. Of course, other methods for removing hydrogen fluoride from the exhaust gas 14 are conceivable. It is also possible that the exhaust gas 14 is added to the reactor through the discharge device 44, where the hydrogen fluoride reacts, for example, with organic matter.

[0129] Fluoride concentration c was identified using a fluoride detector 15. F .

[0130] A leaching device 46 is arranged after the reactor 40 along the direction of material flow M, wherein the material 16 is digested by leaching, for example, with water.

[0131] In the direction of material flow M, a graphite recovery device 48 is arranged after the leaching device 46, wherein, in the present case, the graphite recovery device only has a graphite separation device 22 in the form of a filter. No optional rinsing device for washing away the adhering leaching solution from the graphite is shown. Alternatively, the graphite may be first filled into a transport container, and then the adhering leaching solution may be rinsed off after transport to another location.

[0132] A copper extractor 50 is arranged downstream of the graphite recovery unit 48 in the direction of material flow M. According to a first alternative, the copper extractor includes: a container 52 for cementing copper after the addition of iron (particularly in the form of iron sheets or filings), and a precipitate separator 54 for separating selected copper compounds. The precipitate separator 54 may be, for example, a filter. The pore size of the filter is preferably less than 50 micrometers and at least 1 micrometer.

[0133] According to an alternative embodiment, the precipitate separator is designed to separate copper sulfide, and container 52 is used for the reaction of feed fluid 24 with NaHS, causing copper sulfide to precipitate.

[0134] In the direction of material flow, an Fe / Al / Ti separator 56 is arranged after the copper extractor 50, wherein an oxidant 58 is added to the copper-removing feed fluid 26 in the separator. This may occur in the first container 60.1. The resulting solution is then transferred, for example, pumped into a second container 60.2. In this second container 60.2, a hydroxide, particularly an alkaline hydroxide, is added. For example, sodium hydroxide is added. This results in the precipitation of aluminum, iron, and titanium (if applicable) in the form of hydroxides or hydrated oxides. The precipitate is removed by means of a particle separator 62 arranged downstream in the direction of material flow. The particle separator 62 is formed, for example, by a filter, which may have a maximum pore size of 15 micrometers.

[0135] The resulting pure fluid 28 is added to a solvent extraction apparatus 64 having a Co / Ni solvent extraction device 66. This apparatus includes multiple reaction vessels 38.1, 38.2... interconnected, as shown in the figure. The structure of the solvent extraction apparatus is known from the prior art and will not be described in further detail. This produces a target fluid 32 containing manganese.

[0136] Adding the target fluid 32 to the manganese solvent extraction device 70 generates the target fluid 34.

[0137] According to an alternative, a target fluid 32 containing manganese is added to a second precipitation reactor 72, wherein manganese is precipitated as manganese-hydroxide after the addition of a hydroxide, particularly an alkaline hydroxide such as sodium hydroxide.

[0138] According to the third alternative, a target fluid 32 containing manganese is added to a concentrator 74. Following the addition of carbonates, particularly sodium carbonate, the manganese precipitates or separates as manganese carbonate.

[0139] Lithium precipitates as a carbonate in a suitable container by adding sodium carbonate, or as a phosphate by adding sodium phosphate. The recovery device 36 may include a concentrator 74 for removing water from the target fluid 34 to promote precipitation.

[0140] Figure 3 A flowchart of a method according to the present invention for processing pulverized materials and / or electrode materials that do not contain cobalt, nickel, and manganese is shown. It should be noted that this method corresponds to the method according to... Figure 1 The method has omitted the steps related to the extraction of cobalt, nickel, and manganese.

[0141] Figure 4A flowchart is shown for processing pulverized materials and / or electrode materials that do not contain cobalt and nickel but do contain manganese. For manganese extraction, only variations with solvent extraction are described. Figure 1 and 2 The alternative solutions shown are for removing manganese according to Figure 4 The method described above is also feasible and represents a preferred embodiment.

[0142] Figure 5 A flowchart is depicted for a method of processing electrodes and / or pulverized materials that do not contain manganese and nickel but contain cobalt.

[0143] Figure 6 A flowchart of a method for an electrode and / or a pulverized material according to the present invention is shown, wherein the electrode and / or the pulverized material is free of manganese but contains cobalt and nickel.

[0144] Figure 7 A second embodiment of the recycling device 36 according to the invention is depicted, wherein, for clarity, the components arranged after the leaching device 46 in the direction of material flow have been omitted.

[0145] It should be recognized that the recycling equipment 36 includes a crushing unit 118 and a deactivation device 126. The deactivation device 126 is designed as a drying device.

[0146] First, the lithium batteries 110.1, 110.2... are discharged in discharge unit 112, particularly battery systems consisting of multiple battery modules or battery packs, which in turn consist of multiple battery cells. If necessary, the lithium battery 110 is disassembled at disassembly station 114 because, due to geometric or weight reasons, the battery system could not originally be transported to crushing unit 118. Therefore, where appropriate, the battery system is opened and disassembled to the point where modules and / or battery packs can be removed individually. If necessary, the individual lithium battery cells can also be separated from the drive electronics.

[0147] The resulting sub-units (modules / groups) and / or units 116.1, 116.2... are added to the crushing unit 118. For example, the crushing unit 118 may be a rotary shear having at least one rotor and at least one stator. The crushing unit 118 may also include a cutter having one or more rotors.

[0148] The crushing unit 118 crushes the lithium battery 110.i under a protective gas 120, for example, extracted from a protective gas cylinder 122. Alternatively or additionally, liquid nitrogen from a liquid nitrogen source 119 may be injected. The protective gas may be, for example, nitrogen, a rare gas, carbon dioxide, nitrous oxide, or preferably another non-toxic gas.

[0149] During the crushing process, shredded material 124 is generated and then fed into a deactivation device in the form of a deactivation device 126. An airlock 128 is arranged between the crushing unit 118 and the deactivation device 126. The airlock is airtight, which allows the deactivation device 126 to be substantially well separated from the crushing unit 118, thus ensuring airtightness.

[0150] The deactivation device 126 is connected to a vacuum device 129 that includes a vacuum pump 130 and generates a vacuum. p exists in the deactivation device 126. 126 The pressure p is approximately 100 ± 60 hPa, preferably 50 hPa. 126 It should be noted that, within the scope of this specification, a vacuum pump should be specifically understood to mean, generally speaking, a device that generates a vacuum. It is possible, preferred, but not necessary, for a vacuum pump to also function as a compressor, thereby discharging gas from the vacuum pump at pressures greater than ambient pressure.

[0151] exist Figure 7 In the illustrated case, the vacuum pump is a compressor that draws in and compresses the gas 131 present in the deactivation device 126. Alternatively or additionally, the vacuum device 129 may have a jet pump in which a jet medium in liquid form is directed to pass at high speed through at least one Venturi nozzle. The jet medium is preferably alkaline and has a pH value of at least pH 13, and is, for example, a 10% potassium hydroxide solution.

[0152] Vacuum device 129 includes a gas purification device 132 arranged between deactivation device 126 and vacuum pump 130, and in this case has a condenser 134 and / or activated carbon filter 136. The condenser operates at a temperature of, for example, -10°C to condense dimethyl carbonate and ethyl methyl carbonate, and can distribute them to condensate container 138. Furthermore, any water present is separated by freezing. Control valve 140 is designed to operate at pressure p 26 It opens when it becomes too large, and under pressure p 126 Turn off when it becomes too small (i.e., before the predetermined threshold is reached).

[0153] The dried material is preferably moved within the deactivation device 126. This can be achieved by stirring with an agitator 141, such as an anchor agitator or a rod agitator, having, for example, a rod arranged perpendicular to the agitator axis. Alternatively, this can be achieved using a moving drying container.

[0154] Drying the shredded material 124 yields deactivated pulverized material 10, which is added to the mixer 42.

[0155] Alternatively, the transport container 146 is then filled with deactivated pulverized material 10 under vacuum and / or a protective gas atmosphere. The transport container 146 is preferably airtight. It may be possible, but is not necessary, to fill the transport container 146 with an inert gas to bring it to atmospheric pressure before transport. Alternatively, the transport container may also be sealed under vacuum and transported. Instead of the transport container, a vacuum-sealed foil, such as an aluminum compound foil, can be selected.

[0156] The pulverizing unit 118 is supplied with protective gas 120 from the vacuum pump 130 via a flushing line 148. If the vacuum pump 130 also functions as a compressor (as is the case here) (which represents a preferred embodiment), the protective gas 120 can be introduced from a pressurized gas cylinder 150. Optionally or additionally, the protective gas 120 can be released into the surrounding environment after additional cleaning if necessary.

[0157] List of reference numerals

[0158] 10. Crushed materials

[0159] 12 Sulfuric acid

[0160] 14 Exhaust gas

[0161] 15 Fluoride Detector

[0162] 16 Digestion Materials

[0163] 18 Water

[0164] 20 Graphite

[0165] 22 Graphite Separation Device

[0166] 24 Raw material fluid

[0167] 26. Copper removal feed fluid

[0168] 28 Pure fluid

[0169] 30 solutions

[0170] 32. Manganese-containing target fluid

[0171] 34 Target Fluid

[0172] 36 Recycling Equipment

[0173] 38 Electrode Materials

[0174] 40 reactors

[0175] 42 Mixer

[0176] 43. Sulfuric acid supply unit

[0177] 44 Emission devices

[0178] 46 Leaching device

[0179] 48 Graphite Recycling Unit

[0180] 50 Copper Extractor

[0181] 52 containers

[0182] 54 Sediment Separator

[0183] 56 Fe / Al / Ti precipitant separating agent

[0184] 58 Oxidizing Agent

[0185] 60 containers

[0186] 62 Particle Separator

[0187] 64 Solvent Extraction Apparatus

[0188] 66 Co / Ni Solvent Extraction Unit

[0189] 68. Reaction Vessel

[0190] 70 Mn Solvent Extraction Unit

[0191] 72 Precipitation reactor

[0192] 74 Concentrator

[0193] 110 lithium battery

[0194] 114 Dismantling Station

[0195] Unit 116

[0196] 118 Crushing Unit

[0197] 119 Liquid nitrogen source

[0198] 120 Protective Gas

[0199] 124 Shredded materials

[0200] 126 deactivation device

[0201] 128 airlock

[0202] 129 Vacuum Equipment

[0203] 130 Vacuum Pump

[0204] 131 Gas

[0205] 132 Gas purification device

[0206] 134 Condenser

[0207] 136 Activated Carbon Filter

[0208] 138 Condensate container

[0209] 140 control valve

[0210] 141 Mixer

[0211] 146 Transport Containers

[0212] 148 Flushing line

[0213] 150 pressurized gas cylinder

[0214] c F Fluoride concentration

[0215] T A Digestion temperature

[0216] M is the direction of material flow.

Claims

1. A method for recycling lithium batteries, comprising the steps of: (a) digesting a comminuted material (10) comprising a comminuted fraction of an electrode of a lithium battery using concentrated sulfuric acid (12) at a digestion temperature TA of at least 50 °C, thereby producing off-gas (14) and a digested material (16), (b) venting the off-gas (14), and (c) wet-chemically extracting at least one metal component of the digested material (16), (d) wherein the method does not comprise a pyrometallurgical step, (e) wherein the fluoride content in the comminuted material is at least 0.5% by weight, and (f) wherein the digesting is performed until the concentration of water-soluble fluorides (cF) in the digested material (16) is below 100 mg / kg.

2. The method of claim 1, wherein, comprising the step of: leaching the digested material (16) with an aqueous medium.

3. The method according to claim 1, characterized in that the digesting is performed in a way that fluoride components in the form of hydrogen fluoride in the comminuted material enter the off-gas.

4. The method of claim 1, wherein, the digesting is performed until the concentration of water-soluble fluorides (cF) in the digested material (16) is below 10 mg / kg.

5. The method of claim 1, wherein, at least stoichiometrically using the concentrated sulfuric acid (12) during the digesting.

6. The method of claim 3, wherein, comprising the step of: separating hydrogen fluoride from the off-gas (14).

7. The method of claim 1, wherein, comprising the steps of: (a) leaching the digested material (16), and (b) separating graphite (20), thereby producing a raw material fluid (24).

8. The method of claim 7, wherein, comprising the step of: separating copper from the raw material fluid (24), thereby obtaining a copper-depleted raw material fluid (26).

9. The method of claim 8, wherein, comprising the step of: (a) oxidizing Fe ions in the decopperized feed stream (26) to Fe 2+ 3+ ions, and​ (b) precipitating iron and / or aluminum and / or titanium, thereby obtaining a pure fluid (28).

10. The method of claim 9, wherein, comprising the steps of: (a) solvent extraction of cobalt, and / or (b) solvent extraction of nickel, and / or (c) removal of manganese, thereby obtaining a target fluid (34).

11. The method of claim 10, wherein, comprising the steps of: (a) when the pure fluid (28) comprises cobalt, nickel and / or manganese, precipitating lithium from the target fluid (34); (b) when the pure fluid (28) comprises neither cobalt, nickel nor manganese, precipitating lithium from the pure fluid (28).

12. The method of claim 1, wherein, comprising the steps of: (a) comminuting a battery thereby obtaining a comminuted raw material, and (b) deactivating the comminuted raw material by drying, thereby obtaining the comminuted material.

13. A recycling plant (36) for processing lithium batteries, having: (a) a comminution unit (118) for comminuting the lithium batteries (110), thereby obtaining a comminuted material (10), (b) a deactivation device (126) for deactivating a battery, thereby obtaining a comminuted material (10), (c) a reactor (40) for digesting the pulverized material (10) containing components of the electrode of the lithium battery at a digestion temperature T of at least 50°C A The pulverized material (10) containing components of the electrode of the lithium battery is then digested with concentrated sulfuric acid (12), (d) a sulfuric acid supply device (43) for adding concentrated sulfuric acid (12) to the comminuted material (10), and (e) a venting device (44) arranged to vent off-gas (14) out of the reactor (40), (f) wherein the recycling plant (36) is set up for automatically performing the method according to claim 1.

14. The recycling plant (36) according to claim 13, characterized in that a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), the graphite recovery device comprising: (a) a graphite separation device (22), and (b) a graphite recovery device (48), (b) a rinsing device for rinsing the graphite from the adhering leaching solution, and (c) the graphite recovery device is arranged behind the reactor (40) in the direction of material flow.

15. The recovery plant (36) according to claim 14, characterized in that (a) a precipitated material separator (54) for separating the precipitated Cu or Cu compounds, and / or (b) an Fe / Al / Ti precipitated material separator (56) for separating the precipitated iron and / or aluminum and / or titanium compounds, and / or (c) a solvent extraction device (64) for (i) solvent extraction of cobalt, and / or (ii) solvent extraction of nickel, and / or (iii) removal of manganese, the solvent extraction device being arranged behind the graphite separation device (22) in the direction of material flow.

16. The recovery plant (36) according to claim 13, characterized in that the reactor (40) is a heated forced mixer.

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