Method for processing accumulator components containing an active material, and corresponding recycling system

Abstract

The invention relates to a method for recycling accumulator (72) components (12) containing an active material, in particular black mass (62), having the steps of: (a) leaching the accumulator components (12), in particular the black mass (62), using a leach solution (16) which contains (i) ammonia (30) and (ii) at least one ammonium compound (NH4X), in particular an ammonium salt, such that at least one metal component (M) is transferred at least partly from the accumulator components (12), in particular the black mass (62), into the leach solution (16), thus forming a pregnant leach solution (20) which contains at least one metal hexammine complex (M(NH3)6, M: metal), and (b) regenerating the pregnant leach solution by removing at least one metal component (M) from the pregnant leach solution (20), in particular from the metal hexammine complex (M(NH3)6), such that a regenerated leach solution (54) is produced. The invention also relates to a corresponding recycling system.

Description

[0001] Methods for processing active material-containing accumulator components and corresponding recycling plant

[0002] The invention relates to a method for recycling active material-containing battery components. In particular, the battery components are shredded material, for example, black mass. The active material-containing battery components are, in particular, components of or for batteries, especially alkaline batteries. The method is specifically a method for recycling battery components.

[0003] According to a second aspect, the invention relates to a recycling plant for the recycling of accumulator components containing active materials, in particular of shredded accumulator material.

[0004] Batteries, especially alkaline batteries such as lithium-ion batteries, contain significant amounts of metallic components that have high economic value. Therefore, methods exist for recycling batteries that can no longer be used as batteries. This involves processing them in such a way that the valuable materials they contain are separated from one another as completely as possible, so that they can be reused. The process also applies to the processing of battery components that are production rejects, such as films coated with active material or batteries themselves.

[0005] For such a process, it is desirable that the metallic components of the accumulator parts have as few impurities as possible after separation.

[0006] It is also desirable that the processing of battery components containing active materials generates as little waste as possible. Furthermore, a minimal CO2 footprint is desirable so as not to unduly diminish the environmental benefits that electric vehicles can offer through the recycling of battery components.

[0007] Methods are known from US 2004 / 0028 585 A1, US 2017 / 0077564 A1 and the article “Acid leaching of mixed spent Li-ion batteries” by Nayl et al., Arabian Journal of Chemistry, 2017, 10, S3632-S3639, in which accumulator components are leached with dilute sulfuric acid.

[0008] EP3517641 B2 describes a process in which fluorine components in material containing comminuted components of lithium battery electrodes are driven off using concentrated sulfuric acid. Subsequent processes are therefore less affected by fluoride ions.

[0009] A process is known from CN109193 057 B in which the active material of the positive electrode is calcined, then ground, and subsequently dissolved in water. An ammonium salt, ammonia dissolved in water, and a reducing agent are added to the resulting solution, forming a solution containing an ammonium complex with lithium, nickel, and cobalt, as well as a manganese- or aluminum-containing solid. This solid is filtered off to obtain a solution containing a manganese or aluminum salt. Ammonia dissolved in water or an ammonium salt solution is added to this solution, forming a solution containing an ammonium complex with manganese and aluminum. The solution containing the ammonium complex with lithium, nickel, and cobalt is mixed with the solution containing the ammonium complex with manganese or aluminum and an alkaline solution, forming a precipitate.

[0010] A process is known from CN108767 354 B in which the positive electrodes are first removed from the accumulator. The active material of the positive electrode is then removed from the aluminum foil serving as a support and roasted with ammonium sulfate. The product thus obtained is leached, and the solids are separated from the liquid. A precipitating agent is added to the liquid, causing all metallic components except lithium to precipitate. The precipitate is filtered off, and lithium is precipitated from the remaining solution as lithium carbonate. The invention is based on the objective of improving the recycling of accumulator components containing active materials.

[0011] The invention solves the problem by a method for recycling active material-containing accumulator components from accumulators, in particular shredded material, preferably black mass, wherein the accumulators in particular comprise or are alkaline accumulators, comprising the steps

[0012] (a) Lying the accumulator components, in particular the black mass, with a leaching solution containing (i) dissolved ammonia and (ii) at least one ammonium compound, in particular an ammonium salt, such that at least one metallic component passes at least partially from the accumulator components, in particular the black mass, into the leaching solution, thus forming a pregnant leaching solution containing at least one metal-hexammine complex,

[0013] (a') optional separation of pregnant leaching solution from the leached accumulator components, and

[0014] (b) Regenerating the leaching solution by removing at least one metallic component from the pregnant leaching solution, in particular from the metal-hexammine complex, so that regenerated leaching solution is obtained. The leached accumulator components may also be referred to as leaching residue.

[0015] According to a second aspect, the invention solves the problem by means of a recycling plant for recycling active material-containing accumulator components from accumulators, in particular shredded material, especially black mass, with

[0016] (a) a leaching reactor which (i) is designed for leaching the accumulator components, in particular the black mass, and (ii) contains a leaching solution containing ammonia and at least one ammonium compound, in particular an ammonium salt, such that pregnant leaching solution is formed during leaching,

[0017] (a') optionally a leaching solution discharge line arranged for the discharge of pregnant leaching solution from the leaching reactor, and

[0018] (b) a regeneration unit configured to regenerate the leaching solution by removing at least one metallic component M from the pregnant leaching solution, resulting in regenerated leaching solution. In particular, the regeneration unit is configured to remove at least one metallic component M bound in the metal-hexammine complex. It is possible, but not necessary, for the metallic component M to be removed as a component of the metal-hexammine complex. It is advantageous if the ammonia from the precipitated metal-hexammine complex is recycled back into the leaching solution during regeneration.

[0019] An advantage of the invention is that the active material-containing accumulator components can be processed with less effort compared to prior art methods.

[0020] Another advantage is that the substances used are largely standard substances that are reliably available in large quantities at low prices.

[0021] It is also advantageous that the leaching solution and / or the ammonia and / or at least one ion exchange material can be recycled, which can minimize the waste produced and increase efficiency.

[0022] A further advantage is that the process is generally robust against any impurities in the accumulator components containing active materials. Many metals form hexammine complexes, so the introduction of such metals leads to their precipitation. If unwanted substances are introduced into the leaching solution and cannot be easily removed, the leaching solution can be replaced with relatively little effort compared to the prior art. Unlike, for example, solvent extraction, the chemicals used are significantly less expensive and / or renewable.

[0023] In the context of this description, recycling is understood in particular to mean that chemical components of the accumulator components are made available for subsequent use, especially for the manufacture of new accumulators.

[0024] An accumulator component is understood to be a component that has been used in an accumulator or is intended for use in an accumulator. Accumulator components specifically include the cathode, particularly the cathode active material, and the anode, particularly the anode active material. For example, production rejects generated during the manufacture of accumulators are accumulator components. In particular, cathode material coated with NMC (lithium nickel manganese cobalt oxide) can be an accumulator component. Black mass is also an accumulator component. Alternatively or additionally, material produced by the mechanical comminution of accumulators consists of accumulator components. An accumulator component can also be, for example, a mixture of black mass and material produced.

[0025] Black mass is understood to be a mixture that contains at least active material from both the anode and the cathode.

[0026] An alkaline battery is a battery in which an alkali metal, in particular alkali metal atoms or alkali metal ions, causes the electrochemical reaction by which electrical energy is stored in the battery. Examples of alkaline batteries include lithium batteries and sodium batteries.

[0027] Regenerating the leaching solution means, in particular, treating the leaching solution so that it can be reused for leaching accumulator components, and preferably is reused for this purpose. Specifically, the leaching solution is circulated. It is possible, but not necessary, for the entire leaching solution to be circulated; in particular, it is possible for a portion of the leaching solution to be withdrawn from the circuit continuously or discontinuously. Preferably, at least 50%, in particular at least 60%, in particular at least 70%, in particular at least 80%, and preferably at least 90% of the leaching solution is regenerated so that it can be reused for leaching accumulator components. The percentages mentioned are by weight.

[0028] Depending on the context, the term "metallic component" refers to either a metal in its solid form or its ions. For example, the metallic component is lithium or lithium ions.

[0029] The active material-containing accumulator components preferably contain at least one metallic component M in the form of nickel, cobalt, and / or manganese. These metals are generally present in ionic form or as part of a compound, for example, in the form of NMC (lithium nickel manganese cobalt oxide). The NMC preferably has the molecular formula LiaNi x MnyCo z O2 with x+y+z=1.

[0030] According to a preferred embodiment, battery components from batteries of the same type are used. For example, only battery components from lithium cobalt dioxide batteries, lithium manganese batteries, lithium nickel manganese cobalt batteries, lithium nickel cobalt aluminum batteries, lithium iron phosphate batteries, or lithium manganese iron phosphate batteries are used in the process. However, it is also possible to process mixtures of different batteries, in particular different lithium-ion batteries, together.

[0031] It is also possible to process accumulator components of accumulators that contain a heavy metal as an electrochemically active metal, for example NiCd or NiMH accumulators, using this method.

[0032] Preferably, accumulator components containing nickel, cobalt, and / or manganese are used. The pregnant leaching solution then contains M(NHs)6 ions, where M denotes the corresponding metal. The formula Me = {nickel, cobalt, manganese} applies.

[0033] An ammonium compound is understood to be a compound containing the ammonium ion NH4. + The ammonium compound can therefore be generally written as NH4X, where X is any anion. The anion X can also be called the counterion X. The anion X can be an inorganic or an organic anion. For example, the anion X is a halide ion, a chalcogenide ion, or a sulfate (SO4) ion. 2- -) ion, hydrogen sulfate (HSO4-) ion, or a CO3 2 '-lon. X preferably denotes exactly one anion, but it is also possible that X denotes 2, in particular exactly 2, 3, in particular exactly 3, or more anions.

[0034] Other ions are also possible. It is particularly advantageous if the counterion is SO4. 2 The '-ion' is used when the leaching solution contains a sulfite as a reducing agent. If the leaching solution is aqueous, which is a preferred embodiment, NH4OH, which forms when ammonia dissolves in the leaching solution, can be used as the ammonium compound. In other words, a leaching solution containing dissolved ammonia, and thus ammonium hydroxide, but no other ammonium compound, can be used. Alternatively or additionally, the leaching solution contains an ammonium salt.

[0035] Preferably, the ammonium ion concentration is at least 0.1 mol per liter, in particular at least 0.5 mol per liter, in particular at least 1.5 mol per liter, in particular at least 2.0 mol per liter, for example 5.33 ± 0.15 mol per liter. Preferably, the ammonium ion concentration is at most 23 mol per liter, in particular at most 20 mol per liter, in particular at most 16 mol per liter.

[0036] The active material is the material that participates in the electrochemical reaction by which the battery stores electrical energy. In particular, the oxidation state of the active material changes during charging and discharging. The active material consists specifically of the anode active material and the cathode active material.

[0037] According to one embodiment, regenerating the leaching solution comprises the following step (b1): introducing ammonia, particularly gaseous ammonia, into the pregnant leaching solution and / or cooling the pregnant leaching solution so that a precipitate forms. Particularly preferably, regenerating the leaching solution comprises the following steps: (b2) separating the precipitate from the leaching solution so that depleted leaching solution is obtained, and (b3) lowering the ammonia concentration in the depleted leaching solution, in particular by driving off ammonia from the depleted leaching solution, so that regenerated leaching solution is obtained. Preferably, the method includes the step of heating the depleted leaching solution.

[0038] The advantage of this is that the same substance, namely ammonia, is used both to dissolve at least one metallic component from the accumulator components and to at least partially remove this metallic component from the pregnant leaching solution.

[0039] It is particularly advantageous if the precipitate is used to manufacture new accumulators. According to the invention, therefore, a method for manufacturing an accumulator is also provided in which the anode and / or the cathode is manufactured using the precipitate produced by the aforementioned method.

[0040] A metallic component is understood to include, in particular, metal ions (whose oxidation state or oxidation number is not zero), metal particles, and the metal content in metal salts or metal oxides. For example, at least one metallic component is cobalt, nickel, and / or manganese.

[0041] According to a preferred embodiment, the leaching takes place at a pH of at least pH 5.5, in particular at least pH 6, in particular at least pH 6.5, in particular at least pH 7, in particular at least pH 7.5, and / or at most pH 13, in particular at most pH 12.5, in particular at most pH 12, in particular at most pH 11.5.

[0042] Preferably, battery components containing active materials, specifically lithium nickel manganese cobalt oxide (NMC), are leached. Preferably, the NMC content of the battery components is at least 1.5 wt.%.

[0043] According to a preferred embodiment of the method, accumulator components containing active material are leached, which contain at least 1 wt.%, in particular at least 2 wt.%, in particular at least 3 wt.%, preferably at least 10 wt.%, lithium nickel manganese cobalt oxide (NMC).

[0044] According to a preferred embodiment, the leaching of the accumulator components takes place at a specific leaching temperature. The leaching temperature is preferably at least 100°C, more particularly at least 110°C, and more particularly at least 120°C. Preferably, the recycling plant has a leaching solution temperature control unit for heating the leaching solution to a predetermined leaching temperature.

[0045] It is advantageous if the leaching temperature is chosen such that the lithium nickel manganese cobalt oxide is present in its spinel structure to at least 35% by weight, in particular at least 50% by weight, and preferably at least 60% by weight. There is evidence that NMC can be leached particularly well in its spinel structure. For the molecular formula LiaNi x Mn y CozO2 of lithium nickel manganese cobalt oxide 0.775 < x < 0.825 and 0.075 < y < 0.125 and 0.075 < z < 0.125, in particular 0.785 < x < 0.815 and 0.085 < y < 0.115 and 0.085 < z < 0.115, with x+y+z=1 (NMC811), then the leaching temperature is preferably at most 220°C, in particular at most 210°C. The pressure is preferably chosen such that the lye does not boil.

[0046] The leaching temperature is preferably at least 230°C, in particular at least 240°C, and in particular at least 250°C. If, as provided in a preferred embodiment, active material-containing accumulator components are leached, which contain at least 10 wt.%, in particular at least 20 wt.%, in particular at least 30 wt.%, in particular at least 40 wt.%, in particular at least 50 wt.%, in particular at least 60 wt.%, and in particular at least 70 wt.%, lithium nickel manganese cobalt oxide, for whose molecular formula Li a Ni x Mn y Co z O2

[0047] 0.475 < x < 0.525 and 0.275 < y < 0.325 and 0.175 < z < 0.225, in particular 0.485 < x < 0.515 and 0.285 < y < 0.315 and 0.185 < z < 0.215, with x+y+z=1 (NMC532), then the leaching temperature is preferably at most 320°C, in particular at most 300°C. The pressure is preferably chosen such that the lye does not boil.

[0048] If, as provided according to a preferred embodiment, active material-containing accumulator components are leached, which contain at least 1 wt.%, in particular at least 2 wt.%, in particular at least 3 wt.% lithium nickel manganese cobalt oxide, for whose molecular formula Li a NixMn y CozO2

[0049] If 0.11 < z, in particular 0.15 < z, then the leaching solution is preferably an ammonium carbonate solution. An ammonium carbonate solution is understood to be, in particular, a solution in which the proportion in mol% of ammonium carbonate to all ammonium compounds in the leaching solution is at least 75 mol%, in particular at least 85 mol%.

[0050] If, as provided according to a preferred embodiment, active material-containing accumulator components are leached, which contain at least 1 wt.%, in particular at least 2 wt.%, in particular at least 3 wt.% lithium nickel manganese cobalt oxide, for whose molecular formula Li a NixMn y If the CozO2 z < 0.15, and in particular z < 0.2, the leaching solution is preferably an ammonium sulfate solution. The leaching is preferably carried out in batches. For this purpose, for example, the accumulator components to be leached and the leaching solution are first placed in a reactor, which is then heated to the leaching temperature. After leaching, the temperature is preferably lowered so that the pressure in the reactor drops.

[0051] The ammonia introduced into the pregnant leaching solution acts as a displacement agent. In other words, the ammonia causes displacement crystallization, leading to the formation of the precipitate. Ammonia is not a precipitating agent, as it does not necessarily become a component of the precipitate. While the precipitating hexammine complexes that form the precipitate contain ammonia, these ammonia molecules need not be the same ones introduced into the pregnant leaching solution. Rather, the introduction of ammonia increases the ammonia concentration in the pregnant leaching solution, thereby reducing the solubility of the existing hexammine complexes, resulting in a supersaturated solution and the formation of the precipitate.

[0052] A precipitating agent, on the other hand, would react with the solvated metal components and become part of the precipitate. In other words, the introduced ammonia preferably does not cause precipitation crystallization.

[0053] According to a preferred embodiment, when ammonia is introduced, sufficient ammonia is added to precipitate at least 5 mol%, in particular at least 10 mol%, in particular at least 15 mol%, preferably at least 20 mol%, and most preferably at least 50 mol% of the dissolved metal components. If at least 5 mol% precipitate, this means, in other words, that at least 5 out of every 100 metal ions in the leaching solution are precipitated.

[0054] According to a preferred embodiment, when ammonia is introduced, sufficient ammonia is added to raise the pH value to at least pH 10, and in particular to at least pH 11. In this way, a particularly high proportion of the metallic components in the metal-hexammine complex is precipitated.

[0055] According to a preferred embodiment, the precipitate is a salt of the metallic component, in particular a nickel, cobalt, and / or manganese salt. For example, the precipitate is a carbonate, sulfate, hydroxide, and / or oxide of the metallic component.

[0056] According to a preferred embodiment, sufficient ammonia is introduced such that the solubility of the metal-hexammine complex changes by at least a factor of 1, in particular at least a factor of 1.5, at least a factor of 2, preferably a factor of 5, and particularly preferably a factor of 10. This means that the higher solubility divided by the lower solubility is at least the specified factor.

[0057] According to a preferred embodiment, sufficient ammonia is introduced to achieve an ammonia concentration of at least 7% by weight, in particular at least 8% by weight, preferably at least 9% by weight.

[0058] Separation refers specifically to the removal of the precipitate from the leaching solution. Examples of separation include filtering, centrifuging, or decanting.

[0059] Lowering the ammonia concentration in the depleted lye solution can be achieved, for example, by adding liquid with a lower ammonia concentration or by driving off ammonia.

[0060] The term "driving off" ammonia refers specifically to causing ammonia, particularly as a gas, to leave the leaching solution. This can be achieved, for example, by increasing the temperature of the leaching solution, decreasing its pressure, or by passing an inert gas through it. An inert gas is a gas that does not react with either the ammonia or the ammonium salt. Examples of inert gases include nitrogen, noble gases, and organic gases, such as gaseous alkanes or alkenes.

[0061] Preferably, the pressure for driving off is reduced to, for example, at least 950 mbar absolute, and in particular to at least 800 mbar absolute. Alternatively or additionally, the temperature of the depleted leaching solution is increased by at least 5 Kelvin, and in particular by at least 10 Kelvin. Regenerated leaching solution is understood to be a leaching solution that can subsequently be used again for leaching accumulator components and is used as such. However, it is also possible that the leaching solution is not reused, in whole or in part, for leaching accumulator components, but is, for example, disposed of.

[0062] According to one embodiment, the regenerated leaching solution is used again for leaching accumulator components after regeneration.

[0063] According to one embodiment, the pregnant leaching solution, from the time the ammonia is introduced until the precipitate is separated, has a precipitation temperature of at most 20 °C, particularly at most 15 °C, and especially at most 10 °C, at least temporarily. It has been found that the lower the temperature, the greater the amount of precipitate. Preferably, the precipitation temperature is higher than the freezing point of the leaching solution.

[0064] The solubility of ammonia in water also decreases with temperature, so it is advantageous if the temperature when introducing the ammonia is as low as possible, preferably less than 50°C, particularly less than 40°C, particularly less than 30°C, particularly less than 20°C, particularly less than 10°C, particularly less than 5°C.

[0065] According to a preferred embodiment, a reducing agent is added to the leaching solution before the accumulator components are leached. Alternatively or additionally, the leaching solution contains a reducing agent. A reducing agent is understood to be a substance whose electrochemical potential at the pH, temperature, and pressure present during the leaching process is at most +1.92 volts.

[0066] The reducing agent is preferably selected from the group comprising: (i) hydrogen peroxide, (ii) hydrazine, in particular hydrazine hydrate, (iii) hydroxylamine, (iv) sulfite, in particular an alkali metal sulfite, for example sodium sulfite or ammonium sulfite, (v) hydrogen peroxide and (vi) ammonium formate.

[0067] However, it has been shown that it can be advantageous if the leaching solution does not contain a reducing agent. This is particularly the case if the chemical elements forming the metal-hexammine complex are present at least predominantly (in mol percent), preferably at least 70 mol percent, preferably at least 80 mol percent, preferably at least 90 mol percent, with an oxidation state of +2.

[0068] According to a preferred embodiment, battery components are processed which are predominantly, preferably at least 90% by weight, and in particular at least 95% by weight, not components of lithium iron phosphate batteries. It has been shown that iron ions dissolve poorly, making efficient alkalinization virtually impossible.

[0069] According to a preferred embodiment, the accumulator components, in particular the material to be ground, especially the black mass, are not thermally oxidized and / or calcined before leaching. Thermal oxidation is understood to mean oxidation with the supply of gaseous oxygen (for example, air, an oxygen-containing gas mixture, pure oxygen, or ozone) at a temperature high enough that oxygen reacts with at least parts of the accumulator components, in particular the material to be ground, especially the black mass.

[0070] According to a preferred embodiment, the process comprises the step of removing the conducting salt solvent, in particular organic carbonates, and / or the conducting salt itself. This can be achieved, for example, by means of a washing solvent and / or by evaporation or vaporization and / or by pyrolysis. It is possible to use one, two, or three of these methods. Pyrolysis is defined as heating in the absence of oxygen to a temperature at which the conducting salt and / or binder and / or conducting salt solvent decompose. The binder is a chemical substance by which the active material is bonded to a support. Preferably, ethylene carbonate (EC), if present in the accumulator components, is also removed, preferably to at least 50% by weight.

[0071] According to a preferred embodiment, black mass and / or anode active material and / or cathode active material are leached. Black mass is a component of the accumulator and also comminution material. Black mass is understood to be, in particular, the material obtained by a separation process in which anode active material and / or cathode active material are separated from other components of the accumulator, especially a carrier film. Specifically, the black mass contains anode active material and / or cathode active material. Alternatively, it is possible to leach only anode active material or only cathode active material. Preferably, the black mass contains at least 28 wt.% graphite, but this is not necessary.

[0072] According to a preferred embodiment, the pregnant leaching solution is not mixed with an acid before the ammonia is introduced. In particular, the pH of the pregnant leaching solution changes by at most pH 1 after leaching and before the ammonia is introduced, and more specifically by at most pH 0.5.

[0073] According to a preferred embodiment, the accumulator components, in particular the material to be shredded, especially the black mass, are leached directly, particularly in a chemically unchanged state, particularly unroasted. This contributes to a small CO2 footprint of the process.

[0074] Particularly when the CO2 footprint of the process is not a primary concern, chemically modified, especially roasted, crushed material can also be treated with lye. According to one embodiment, the process then comprises the steps of: removing binder from the black mass, particularly by heating or using a binder solvent, and lye the black mass thus obtained.

[0075] According to a preferred embodiment, gaseous ammonia is introduced into the pregnant leaching solution. In this way, the ammonia concentration in the pregnant leaching solution can be increased simply and effectively. Alternatively or additionally, the ammonia is introduced by introducing an ammonia solution, particularly an aqueous one, whose ammonia concentration is higher than that of the pregnant leaching solution.

[0076] According to a preferred embodiment, such a large amount of ammonia is introduced that the quotient of the amount of substance (in moles) of nickel precipitated by the introduction of the ammonia as the numerator and the amount of substance (in moles) of nickel in the pregnant leaching solution before the introduction of the ammonia as the denominator is at least 0.4, in particular at least 0.5, in particular at least 0.6, in particular at least 0.7, in particular at least 0.8, in particular at least 0.9.

[0077] According to a preferred embodiment, such a large amount of ammonia is introduced that the quotient of the amount of substance (in moles) of cobalt precipitated by the introduction of the ammonia as the numerator and the amount of substance (in moles) of cobalt in the pregnant leaching solution before the introduction of the ammonia as the denominator is at least 0.4, in particular at least 0.5.

[0078] According to a preferred embodiment, enough ammonia is introduced to change the pH value by at least 0.25, in particular by at least 0.5, in particular by at least 1.

[0079] According to a preferred embodiment, the precipitate is at least substantially oxalate-free. Accordingly, the reagent that triggers the precipitate is preferably defined as follows: The characteristic that something is substantially oxalate-free is understood in particular to mean that the concentration of oxalate-free components is less than 10 wt.%, in particular 5 wt.%, and in particular 1 wt.%.

[0080] According to a preferred embodiment, the ammonia is introduced into the pregnant leaching solution in such a way that the precipitate forms by displacement crystallization. Displacement crystallization is understood to be a process in which the crystallization of a compound or several compounds, such as a salt or several salts, is caused by a change in the mixing ratio of the individual components of the solvent mixture. Changing the mixing ratio of water to ammonia results in a decrease in the solubility of the metal-hexammine complex.

[0081] The introduction of ammonia is preferably not a precipitation reaction in which the addition of another component, here ammonia, causes a chemical reaction between the component to be precipitated, here the metallic component, and the added component to form a sparingly soluble compound. This is because, prior to the introduction of the ammonia, metal-hexammine complexes are already present in the leaching solution, which precipitate unchanged as complex salts upon the introduction of ammonia. Therefore, no chemical reaction takes place. Instead, the introduction of ammonia alters the solubility of the water-ammonia mixture for the complex salts. Strictly speaking, the leaching solution contains a salt of the metal-hexammine complex M(NHs)6. The anion of this salt is designated X. However, since this salt is dissolved, the present description refers only to the metal-hexammine complex.

[0082] According to one embodiment, the method comprises the step of removing lithium from the pregnant leaching solution before introducing ammonia. The removal of lithium from the pregnant leaching solution is carried out before or after any removal of copper. The lithium is preferably removed by means of an ion exchanger.

[0083] According to one embodiment, regenerating the leaching solution comprises the following steps: (i) contacting the pregnant leaching solution with at least one ion exchange material to selectively remove a metallic component, in particular lithium, from the pregnant leaching solution, resulting in selectively depleted leaching solution, and (ii) separating the selectively depleted leaching solution and the ion exchange material. Preferably, the method includes step (iii) regenerating the ion exchange material to obtain a compound of the metallic component and regenerated ion exchange material.

[0084] Preferably, the first ion exchange material is selective for at most 3, in particular at most 2, and more preferably at most one metallic component. This means that the ion exchange material, from a pregnant leaching solution containing lithium ions, cobalt ions, nickel ions, and manganese ions in equal molar proportions, absorbs at least three times, in particular at least four times, in particular at least five times, preferably at least six times, most preferably at least seven times, and most preferably at least ten times, as much of the corresponding metallic component as it absorbs of the other metallic components for which the ion exchange material is not selective. It is particularly advantageous if the first ion exchange material is selective only for lithium.

[0085] The ion exchange material can be added to the pregnant leaching solution, for example, as granules. In this case, separating the selectively depleted leaching solution from the ion exchange material is a solid-liquid separation, such as filtration or centrifugation.

[0086] Alternatively, the ion exchange material can be in the form of a stationary object, for example, an ion exchange column. In this case, the separation of the selectively depleted leaching solution and the ion exchange material occurs through the flow of the leaching solution past the ion exchange column.

[0087] Regenerating the ion exchange material is achieved, for example, by bringing it into contact with an acid, causing the bound metallic component to dissolve from the ion exchange material. The at least one metallic component can then be separated, for example, as a salt of the acid used. The regenerated ion exchange material is preferably reused for the selective removal of the metallic component from the pregnant leaching solution.

[0088] Preferably, the metallic component is lithium. In particular, lithium ions are bound by the ion exchange material. Typically, the ion exchange material releases one proton into the leaching solution for each lithium ion absorbed. The metallic component can also include cobalt, nickel, and / or manganese ions.

[0089] Hydrogen titanium oxide (HTiCh, HTO) is suitable for lithium extraction. For transition metals, chelating cation exchange resins containing iminodiacetic acid as a complexing agent are suitable, for example.

[0090] A suitable ion exchange material is a plastic functionalized with aminophosphonic acid, amidoxime, and / or isothioronium groups. According to one embodiment, the ion exchange material is a plastic functionalized with iminodiacetic acid. This material is selective for Cu, Pb, Ni, Cd, Fe, Mn, and Ca. The plastic is, for example, a polystyrene divinylbenzene resin.

[0091] Preferably, the regeneration of the leaching solution comprises the step of removing copper from the pregnant leaching solution and / or the selectively depleted leaching solution, in particular by electrolysis or cementation. According to one embodiment, the regeneration of the leaching solution includes the following step: (i) bringing the selectively depleted leaching solution into contact with at least a second ion exchange material for the selective removal of at least a second metallic component, in particular nickel, cobalt, and / or manganese, from the selectively depleted leaching solution. Preferably, this results in the regenerated leaching solution.

[0092] Preferably the process comprises the step (ii) of separating the leaching solution thus obtained and the at least one second ion exchange material and preferably (iii) of regenerating the at least one second ion exchange material, such that a compound of the at least one second metallic component and regenerated second ion exchange material is obtained.

[0093] According to a preferred embodiment, the method comprises the step of shredding a battery, in particular an alkaline battery, so that shredded material is produced. It is possible that this shredded material is then treated with an alkaline solution, particularly after sorting. Sorting is understood to mean the separation of plastic parts and / or housing parts and / or metal foil parts and / or plastic films (for example, separator films).

[0094] Alternatively, the process includes the step of separating the black mass from the material being ground. In other words, the material being ground is separated into a first fraction and at least one second fraction, the first fraction being the black mass. The second fraction contains, in particular, housing parts and separator film fragments.

[0095] According to the invention, a method for recycling accumulators is particularly relevant, comprising the step of shredding at least one accumulator, especially an alkaline accumulator, to produce shredded material, and the steps of the method according to the first aspect. The method preferably includes the step of separating black mass from the shredded material. The accumulators can be used accumulators or, for example, production rejects.

[0096] According to a preferred embodiment, the method comprises the step of adding the ammonium compound, in particular ammonium salt, to the leaching solution. Preferably, the ammonium compound, in particular the ammonium salt, is added after the precipitate has been separated. For example, the ammonium compound is added to the regenerated leaching solution. In particular, sufficient ammonium compound is added to achieve a predetermined target ammonium ion concentration in the leaching solution.

[0097] Preferably, the desired ammonium ion concentration is at least 0.1 mol per liter, in particular at least 0.5 mol per liter, in particular at least 1.5 mol per liter, in particular at least 2.0 mol per liter, for example 5.33 ± 0.15 mol per liter. Preferably, the desired ammonium ion concentration is at most 23 mol per liter, in particular at most 20 mol per liter, in particular at most 16 mol per liter.

[0098] According to a preferred embodiment, the method comprises the step of reusing the regenerated leaching solution to leach accumulator components, in particular crushed material, especially black mass. In other words, the leaching solution is circulated.

[0099] According to one embodiment, the active material-containing accumulator components are leached with a leaching solution at a temperature of at least 10 °C and / or at most 300 °C. These temperatures have proven suitable. Alternatively or additionally, the active material-containing accumulator components are leached at a pressure (pu) of at least 6 bar and / or at most 35 bar.

[0100] According to one embodiment, the process comprises the step of adding a sulfate ion-forming agent, in particular sulfuric acid or a sulfuric acid-forming substance such as sulfur trioxide or disulfuric acid, to the leaching solution. Preferably, the sulfuric acid is added after the precipitate has been separated. This is particularly advantageous if the ammonium compound NhX is a sulfate and / or the precipitate is or contains a sulfate. The reaction of the acid with the leaching solution is generally exothermic, which leads to a desirable heating of the leaching solution. If the acid is sulfuric acid, it preferably has a concentration of at least 20%, in particular at least 40%, and most preferably at least 80%. The acid is preferably added after the precipitate has been separated and / or before the accumulator components have been leached.According to one embodiment, the process includes the step of adding carbon dioxide (CO2) to the leaching solution. This forms carbonic acid. This is particularly advantageous if the precipitate is or contains a carbonate. The CO2 is preferably added after the precipitate has been separated and / or before the accumulator components have been leached. Preferably, the carbon dioxide is added to the leaching solution after copper, cobalt, nickel, and / or manganese ions, and optionally cadmium and / or mercury, have been removed. This results in the precipitation of pure lithium carbonate, which is uncontaminated or only minimally contaminated with other carbonates.

[0101] If the precipitate contains a carbonate, the CO2 can be generated, according to a preferred embodiment, by burning, i.e., heating, the precipitate. In this way, a CO2 cycle can be established.

[0102] According to one embodiment, the method comprises the step of leaching the accumulator components, in particular the black mass, with a leaching solution containing at least one lithium-extracting substance. A lithium-extracting substance is understood to be a substance that dissolves the lithium from the accumulator components, wherein the lithium leaching power is preferably greater, in particular by at least a factor of 1.5, in particular by a factor of 3, preferably at least 3, than the nickel leaching power and / or the cobalt leaching power and / or the manganese leaching power.

[0103] The leaching capacity is the quotient of the content of the respective component (e.g., lithium) in the battery components in mole percent before the first leaching (as the denominator) and the decrease in the content of the respective component (e.g., lithium) in the battery components after the first leaching (as the numerator). For example, if 20 mole percent of the lithium is leached during the first leaching, then the leaching capacity of the lithium-extracting substance is 20%.

[0104] The lithium-extracting substance contains, for example, carbonic acid, supercritical CO2, and / or a moderately strong or weak acid. A moderately strong acid is understood to be, in particular, an acid having a pKa value of 1 or more and less than 4.7; a weak acid is understood to be, in particular, an acid having a pKa value greater than 4.7. Preferably, the moderately strong or weak acid is an organic acid, for example, formic acid, acetic acid, propanoic acid, butyric acid, or citric acid.

[0105] According to one embodiment, the method includes the step of adding a substance that changes the oxidation state (which is equivalent to the oxidation number) of the metallic component.

[0106] For example, the process includes the step of adding an oxidizing agent to the pregnant leaching solution. When leaching the battery components, it can be advantageous for the metal ions in the metal-hexammine complex to have a low oxidation state. Conversely, a comparatively higher oxidation state can be advantageous in order to precipitate as much of the metallic component, especially cobalt, as possible. The oxidizing agent is preferably a liquid oxidizing agent, for example, hydrogen peroxide. Alternatively, a gaseous oxidizing agent, for example, ozone, can also be used.

[0107] According to a preferred embodiment, the leaching of the active material-containing accumulator components, in particular the material to be comminuted, especially the black mass, takes place at a temperature of at least 10°C and / or at most 320°C, particularly at most 300°C, preferably at most 250°C, particularly preferably at most 200°C, particularly preferably at most 175°C, and particularly preferably at most 150°C. This has proven to be a good compromise between a sufficiently high reaction rate and a high level of equipment complexity.

[0108] Preferably, the leaching of the active material-containing accumulator components, in particular the material to be comminuted, especially the black mass, is carried out at a pressure of at least 1.5 bar (0.15 MPa), in particular at least 3 bar, in particular at least 5 bar, in particular at least 6 bar and / or at most 100 bar, in particular at most 70 bar, in particular at most 50 bar, preferably at most 35 bar. If the pressure is too low, little ammonia is introduced into the leaching solution, resulting in little precipitate formation, which is undesirable. If the pressure is too high, the equipment required is complex, which is also undesirable. According to one embodiment, the process includes the step of at least partially removing at least one hydrogen fluoride-forming agent from the active material-containing accumulator components, in particular the black mass, prior to leaching.Hydrogen fluoride formers are substances that release hydrogen fluoride when heated. Removal, in particular, means that at least 50 mol%, especially at least 70 mol%, preferably at least 85 mol%, of the fluorine components are removed.

[0109] The removal of hydrogen fluoride formers can be achieved, for example, by washing with a conducting salt solvent and / or washing with a binder solvent. For example, the conducting salt solvent and / or the binder solvent is or contains DMSO.

[0110] Alternatively or additionally, the removal of hydrogen fluoride producers can involve heating to decompose the conducting salt and / or binder. Preferably, all hydrogen fluoride producers are removed. It has been found that the binder hinders the leaching process. Removing the binder generally results in improved leaching efficiency.

[0111] According to one embodiment, the process comprises the step of washing the active material-containing accumulator components (in particular the comminuted material or the black mass) with a washing solvent so that the conducting salt solvent of the accumulator is removed. This step is carried out before the leaching of the accumulator components. In particular, the washing is carried out such that at least 60 wt.%, in particular at least 70 wt.%, in particular at least 80 wt.%, in particular at least 90 wt.%, preferably at least 95 wt.%, of the high-boiling components of the conducting salt solvent are removed. A high-boiling component is understood to be a substance whose boiling point at 100 hPa is above 80 °C. Ethylene carbonate is, for example, a high-boiling component.Washing out the high-boiling components prevents them or their reaction products, such as ethylene carbonate, from contaminating the leaching solution. This washing solvent can also be called a conducting salt solvent. In particular, this prevents the accumulation of urea in the leaching solution. The conducting salt is, or contains, lithium hexafluorophosphate, for example. The conducting salt solvent is usually a mixture of several substances. Well-known conducting salt solvents are mixtures containing EMC (ethyl methyl carbonate) and DMC (dimethyl carbonate).

[0112] Preferably, the binder is insoluble in the conducting salt solvent.

[0113] According to one embodiment, the process comprises the step of washing the active material-containing accumulator components, in particular the comminuted material, especially the black mass, with a washing solvent so that the conducting salt of the accumulator is removed. This washing solvent can also be referred to as the conducting salt washing solvent. The conducting salt washing solvent can be the same substance or the same mixture of substances as the conducting salt solvent solvent (if this step is carried out), but this is not necessary. For example, the washing solvent is conducting salt solvent that has been extracted from accumulator components, for example by washing or evaporation. Alternatively, the solvent is an alcohol, for example ethanol. Removing the conducting salt improves its recycling. Furthermore, it reduces contamination of the leaching solution by conducting salt.

[0114] Preferably, the binder is insoluble in the conducting salt washing solvent.

[0115] According to one embodiment, the method comprises the step of washing the accumulator components, in particular the black mass containing active material, with a binder solvent, so that binder from the accumulator is removed.

[0116] The binder solvent is preferably a polar solvent, for example dimethyl sulfoxide (DMSO), dimethylformamide, acetone, cyclohexanone, isopropylacetone, 2,5-dimethyl isosorbide, formamide, N-methyl-2-pyridone, N-methyl-2-pyrrolidone, N-methyl-2-piperidone, sulfolane, lactones of ring size 4 or 5 such as 4-hydroxybutyric acid lactone or 4-valerolactone, or mixtures of 2, 3, 4 or 5 of these substances.

[0117] According to one embodiment, the method comprises the step of drying the comminution material, particularly after washing. Especially if the conductive salt has not been removed or not completely removed, it is advantageous to carry out the drying at a temperature of no more than 70°C in order to prevent the evolution of hydrogen fluoride or other fluorine-containing gases as far as possible. This drying is preferably carried out under vacuum, with the minimum pressure reached during drying preferably below 100 hPa, particularly below 50 hPa, and especially below 10 hPa.

[0118] According to one embodiment, the black mass is separated by screening and / or sieving, in particular air jet sieving, of the dried crushed material.

[0119] According to one embodiment, the method comprises the step, after the leaching of the accumulator components to produce leached accumulator components, of re-leaching the leached accumulator components with primary leaching solution that, after the removal of the ammonia, has not yet been used to leach accumulator components or that has never been used for leaching. In other words, the accumulator components, in particular the material to be shredded, especially the black mass, are leached more than once. Preferably, the regenerated leaching solution that, after the removal of the ammonia, has not yet been used to leach accumulator components or that has never been used for leaching (referred to as the primary leaching solution) is used to leach the already leached accumulator components, in particular the accumulator components that have been leached most frequently.

[0120] In particular, the process preferably comprises the following step: after leaching the accumulator components, in particular the washed accumulator components, preferably the washed black mass, so that leached accumulator components, in particular leached black mass, and secondary pregnant leaching solution are produced, leaches of accumulator components that have not yet been leached, in particular black mass that has not yet been leached, with secondary pregnant leaching solution.

[0121] Preferably, the process comprises the step of heating leached battery components, in particular leached black mass, to a phase transition temperature. The phase transition temperature is preferably high enough that at least some of the battery components, in particular lithium nickel manganese cobalt oxide (NMC), change their crystal structure. Preferably, the battery components thus temperature-treated are leached again. It has been found that a temperature treatment of battery components that are initially difficult to leach can increase the leaching rate during the second leaching.

[0122] Preferably, the phase transition temperature is at least 120 °C, particularly at least 140 °C, and especially preferably 150 °C. Preferably, the phase transition temperature is at most 200 °C, particularly at most 180 °C.

[0123] According to one embodiment, the accumulator components, in particular the black mass, are leached at least three times. Preferably, the accumulator components, especially the black mass that has been leached most frequently, are leached with regenerated leaching solution that has not yet been used to leach any black mass. The resulting saturated leaching solution is then used, particularly without subsequent regeneration, to leach black mass that has been leached less frequently.

[0124] In particular, the accumulator components are preferably leached using a countercurrent process. The accumulator components are leached N times successively, and for the nth (n = 1, 2, ..., N) leaching, a leaching solution is used that, after the removal of ammonia, has been used for leaching at most (Nn) times. It is preferred that the leaching of different leaching stages is carried out in separate containers. Preferably, a solid-liquid separation is performed after each leaching stage.

[0125] According to a preferred embodiment, the expelled ammonia is recycled for reintroduction into, in particular, a leaching solution. This means, in particular, that the ammonia is introduced into the leaching solution in the direction of material flow at a point upstream of where the ammonia was expelled. For the leaching solution, the material flow direction ends after the expulsion of the ammonia and before the subsequent leaching. The expelled ammonia is preferably dried before being reintroduced into the leaching solution. The expelled ammonia is preferably compressed and / or liquefied.

[0126] According to a preferred embodiment, the process includes the step of depositing copper from the pregnant leaching solution. This is achieved, for example, by electrolysis or cementation. Electrolysis can also be referred to as electrowinning. Cementation is understood to be the electrochemical deposition of metals from solutions. Cementation can be effected, for example, with a metal having a lower electrochemical potential or with an organic or inorganic reducing agent. In this way, a precipitate is obtained that is particularly recyclable, especially for the production of new active material.

[0127] For example, under suitable conditions, especially metallic nickel, can be used to cement the copper. According to one embodiment, nickel, particularly in the form of nickel powder, is used for cementing. According to the reaction equation Cu 2+ + Ni — > Ni 2++ Cu, copper is deposited. It is advantageous if the pregnant leaching solution is passed through nickel powder. For example, the nickel powder is arranged in a thin tube. A thin tube is understood to be a tube whose length is at least three times its diameter, in particular at least five times, preferably at least ten times. It is especially advantageous if the tube consists of several tube sections that can be separated from each other without damage.It is then possible (in a preferred embodiment of a method according to the invention) to remove a pipe section in which the ratio of nickel to copper has fallen below a predetermined threshold and to connect a pipe section in which the ratio of nickel to copper is above the predetermined threshold, in particular at least 10, preferably at least 100, preferably at least 1000, to the remaining pipe sections, preferably in an upstream direction.

[0128] Preferably, the removal of copper from the pregnant leaching solution comprises first deposition by electrolysis and then by cementation. Deposition by electrolysis is technically simple but time-consuming, especially at low copper concentrations. Cementation, on the other hand, removes even very small amounts of copper but requires regular replacement of the cementation material, which is more complex. Combining both methods provides a simpler and highly effective method for removing copper from the pregnant leaching solution.

[0129] According to a preferred embodiment, the process comprises the step of dissolving binder from the leached black mass using a binder solvent. This solvent may preferably be dimethyl sulfoxide (DMSO), dimethylformamide, acetone, cyclohexanone, isopropylacetone, 2,5-dimethyl isosorbide, formamide, N-methyl-2-pyridone, N-methyl-2-piperidone, sulfolane, or lactones of ring size 4 or 5, such as 4-hydroxybutyric acid lactone or 4-valerolactone, or mixtures of 2, 3, 4, or 5 of these substances. This dissolution of binder from the leached black mass preferably takes place before leaching. According to a preferred embodiment, it is possible, but not necessary, for binder to be dissolved from the leached black mass.

[0130] According to a preferred embodiment, the process comprises the step of dissolving manganese and / or aluminum and / or copper components from the leached black mass. Graphite is obtained in this way. This graphite can be further purified, for example with dilute or concentrated mineral acid, such as sulfuric acid, which is another preferred step.

[0131] Preferably, the manganese and / or aluminum and / or copper components are removed using a volatile acid. A volatile acid is defined as an acid whose boiling point at normal pressure is below 250 °C and / or whose boiling point at 100 hPa is below 150 °C. The low boiling point allows for easy removal of any remaining volatile acid. Preferably, the volatile acid is an organic acid, such as formic acid or acetic acid.

[0132] According to a preferred embodiment, the process comprises the step of heating the precipitate obtained by introducing ammonia so that a nickel-cobalt salt is formed. For example, the precipitate is heated to at least 95°C, particularly at least 120°C, for example T = 150 ± 20°C if it is a carbonate salt, and to at least 280°C if it is a sulfate. Such nickel-cobalt salts can be used for the production of new active material for batteries.

[0133] According to a preferred embodiment, the process comprises the step of adding a manganese compound dissolved in water, in particular a manganese salt, for example manganese sulfate, to the nickel-cobalt salt. Preferably, sufficient manganese compound is added such that an electrode material precursor subsequently produced from the solution has a predetermined manganese concentration.

[0134] According to a preferred embodiment, the method comprises the step of adding a nickel compound dissolved in water, in particular a nickel salt, for example nickel sulfate, to the nickel-cobalt salt. Preferably, sufficient nickel compound is added such that an electrode material precursor subsequently produced from the solution has a predetermined nickel concentration.

[0135] According to a preferred embodiment, the method comprises the step of adding a cobalt compound dissolved in water, in particular a cobalt salt, for example cobalt sulfate, to the nickel-cobalt salt. Preferably, sufficient cobalt compound is added such that an electrode material precursor subsequently produced from the solution has a predetermined cobalt concentration.

[0136] Preferably, this solution is acidic, for example, it contains dilute sulfuric acid. A precursor to an NMC (lithium nickel manganese cobalt oxide) suitable for the production of new accumulators can be obtained from the solution thus obtained.

[0137] According to a preferred embodiment, the process includes the step of removing metallic impurities from the solution formed by the addition of the water-soluble manganese compound. This is done, for example, by ion chromatography and / or cementation. This yields a purified solution. Metallic impurities are understood to be those metallic components that are not intended to become part of the new cathode active material. According to a preferred embodiment, the process includes the step of adding a base to the, in particular purified, solution, so that an active material precursor precipitates. This can be used as a starting material for the production of new cathode active material.

[0138] According to a preferred embodiment, the leaching reactor is operated in batch mode. This has the advantage that the leaching solution and the leached accumulator components can be separated particularly well from each other.

[0139] According to a preferred embodiment, the method comprises the step of evaporating at least a portion of the leaching solution, in particular the regenerated leaching solution, so that a lithium compound, in particular a lithium salt, is obtained. It is advantageous if the evaporated portion of the leaching solution is condensed and reused for leaching the accumulator components. It is possible to evaporate and recondense the entire regenerated leaching solution. However, it is advantageous if only a portion of the leaching solution, in particular the regenerated one, is evaporated. In this way, lithium is removed from the leaching solution cycle and its accumulation is prevented.

[0140] According to one embodiment, the process comprises the steps (i) crushing the accumulators to obtain crushed material, (ii) washing the crushed material with solvent to wash out conducting salt solvent, in particular ethylene carbonate, (iii) drying, (iv) sorting to obtain black mass, and (v) washing out the black mass with binder detergent.

[0141] According to one embodiment, the regeneration system (i) has a precipitation generator, in particular an ammonia injection device, which is designed to treat the leaching solution so that a precipitate forms, in particular by

[0142] Introducing, in particular gaseous, ammonia into the pregnant leaching solution and / or cooling the pregnant leaching solution so that the precipitate forms, wherein the leaching solution discharge line is preferably arranged to supply the pregnant leaching solution to the precipitate generator, (ii) a precipitate separator to separate the precipitate so that depleted leaching solution is obtained, and

[0143] (iii) a regenerator configured to treat the depleted leaching solution such that the solubility of at least one component of the accumulator components, in particular the black mass, is increased, in particular by at least a factor of 2, in particular by at least a factor of 5, in particular by at least a factor of 10.

[0144] Preferably, the regenerator has an ammonia removal device designed to remove ammonia from the depleted leaching solution, resulting in regenerated leaching solution. Preferably, the regenerator includes the ammonia removal device.

[0145] Preferably, the precipitation generator comprises an ammonia injection device and / or a cooler.

[0146] According to one embodiment, the regenerator has a feature designed for the removal of copper, which is configured to drive out ammonia from the depleted leaching solution, resulting in regenerated leaching solution.

[0147] Preferably, the regenerator includes a heater for heating the leaching solution to drive off the ammonia. Alternatively or additionally, the regenerator can be configured to reduce the pressure of the leaching solution and / or to pass an inert gas through it.

[0148] The recycling plant according to the invention preferably has a leaching solution discharge line arranged for conveying pregnant leaching solution from the leaching reactor to the precipitation generator, in particular to the ammonia injection device, and for introducing the pregnant leaching solution into the precipitation generator, in particular the ammonia injection device. Alternatively, it is possible that the leaching of the accumulator components and the separation of the leached accumulator components and the pregnant leaching solution are carried out in a single container. It is also possible that the separation of the leached accumulator components and the pregnant leaching solution and the introduction of ammonia are carried out in a single container. Preferably, the recycling plant also has a return line arranged for conveying regenerated leaching solution from the ammonia discharge device to the leaching reactor.

[0149] The recycling plant according to the invention is preferably designed to carry out a process according to the invention.

[0150] According to one embodiment, the regeneration system has a lithium extractor for removing lithium from the pregnant leaching solution. The lithium extractor is arranged upstream of the ammonia injection device in the direction of material flow of the leaching solution. Alternatively, the lithium extractor is arranged upstream of any copper separator that may be present.

[0151] The recycling plant according to the invention preferably has a shredding unit for shredding accumulators. The shredding unit is understood to be, in particular, a device that shreds the batteries during operation. For example, the shredding unit is (i) a pressure shredding unit in which the batteries are crushed between two tool surfaces, (ii) an impact shredding unit in which the batteries rest on a tool surface and are shattered by impact with a second moving tool, (iii) a shear shredding unit in which the batteries are shredded by two opposing moving tool surfaces, (iv) a cutting shredding unit in which the batteries are cut into two pieces by means of two cutting edges, and / or (v) an impact shredding unit in which the batteries are thrown against a wall, collide with a moving tool, or two particles collide with each other.Naturally, the comminution unit can also operate using two or more of the aforementioned comminution mechanisms. According to a preferred embodiment, the comminution unit is part of a comminution device that includes a container in which the comminution unit is arranged.

[0152] The recycling plant according to the invention preferably has a separation device for separating black matter from the shredded material. For example, the separation device comprises a magnetic separation device and / or a classifier, in particular a cross-flow classifier and / or a zigzag classifier.

[0153] The recycling plant according to the invention preferably comprises a feeder configured for adding ammonium salt to the, in particular regenerated, leaching solution. Preferably, the feeder is configured for automatically measuring the ammonium salt concentration, for example by measuring the electrical conductivity, and for automatically feeding the ammonium salt so that a predetermined target ammonium compound concentration is established. The feeder is part of the regenerator.

[0154] The recycling plant according to the invention preferably has a scrubber designed for washing the black mass with a washing solvent, so that conducting salt solvent from the accumulator is removed. The scrubber is connected to the leaching reactor so that the washed black mass can be fed to the leaching reactor.

[0155] Alternatively or additionally, the scrubber is equipped to wash the black mass with washing solvent, so that conducting salt from the accumulator is removed.

[0156] The recycling plant according to the invention preferably has a copper separator arranged for separating copper from the pregnant leaching solution. For example, the copper separator is an electrolysis cell for separating metallic copper.

[0157] According to a preferred embodiment, the recycling plant comprises a solid-liquid separator for separating the pregnant leaching solution from the leached accumulator components, in particular the leached black mass, i.e., from the leaching residue. For example, the solid-liquid separator comprises a sieve and / or a centrifuge and / or a decanter. The solid-liquid separator can, for example, be part of the leaching reactor or be physically separate from the solid-liquid separator.

[0158] According to a preferred embodiment, the recycling plant comprises a leaching tank. It is advantageous if the leaching reactor is designed for batch operation. According to one embodiment, the regeneration plant includes an ion exchange unit configured and arranged for (i) contacting the pregnant leaching solution with an ion exchange material for the selective removal of at least one metallic component, in particular exactly one metallic component, especially lithium, from the pregnant leaching solution, so that selectively depleted leaching solution is obtained, (ii) separating the selectively depleted leaching solution and the ion exchange material, and preferably (iii) regenerating the ion exchange material, so that in particular a compound, for example a salt, of the metallic component and regenerated ion exchange material is obtained.

[0159] Preferably, the regeneration system has a second ion exchange unit designed to bring the selectively depleted leaching solution into contact with at least one second ion exchange material for the selective removal of at least one second metallic component, in particular nickel, cobalt and / or manganese, from the selectively depleted leaching solution, separation of the leaching solution thus obtained and the at least one second ion exchange material, and preferably regeneration of the second ion exchange material, so that a compound of the at least one second metallic component and regenerated second ion exchange material is obtained.

[0160] Preferably, the regeneration system is designed to remove copper from the pregnant leaching solution, particularly by electrolysis or cementation. Strictly speaking, copper removal refers to the removal of copper ions from the pregnant leaching solution.

[0161] Alternatively, the copper separator comprises a feeder configured for the automatic feeding of a cementation reagent that effects the cementation of copper. The invention is explained in more detail below with reference to the accompanying drawings. These drawings show...

[0162] Figure 1 shows a flowchart of a process according to the invention and a schematic representation of a recycling plant according to a first embodiment according to the invention.

[0163] Figure 2a shows a flowchart of a process according to the invention and a schematic representation of a recycling plant according to a second embodiment according to the invention.

[0164] Figure 2b shows a flowchart of a process according to the invention and a schematic representation of a recycling plant according to a third embodiment according to the invention.

[0165] Figure 3 shows a flowchart of a process according to the invention and a schematic representation of a recycling plant according to a fourth embodiment according to the invention.

[0166] Figure 4 shows a recycling plant according to the invention in a fifth embodiment,

[0167] Figure 5 shows a recycling plant according to the invention in a sixth embodiment and

[0168] Figure 6 shows a recycling plant according to the invention in a seventh embodiment.

[0169] Figure 1 shows a flow diagram of a recycling plant 10 according to the invention for recycling accumulator components 12 containing active materials. The recycling plant 10 has a leaching reactor 14 containing a leaching solution 16. It is possible, but not necessary, for the leaching reactor 14 to have a stirrer 18 by means of which the leaching solution 16 and the accumulator components 12i (i = 1, 2, ...) contained therein can be moved. The accumulator components contain at least one metallic component M, where M can be, for example, cobalt, nickel, and / or manganese. In particular, M can also represent two or more metallic components. The pressure pu in the leaching reactor 14 is, for example, between pi4 = 10...30 bar. For example, a leaching temperature T14 is Ti4 = 50... 120 °C, but it can also be significantly higher.

[0170] For example, leaching solution 16 is an aqueous solution containing 2.67 moles per liter of an ammonium compound NH4X, here in the form of an ammonium salt, ammonium sulfate (NF₄SCU). Leaching solution 16 also contains 2.67 moles per liter of dissolved ammonia NH₃. The leaching temperature can be, for example, Tu = 70 °C. The pressure pu can be, for example, pu = 7 bar. Other concentrations, temperatures, and pressures are possible, as specified above in the introductory description.

[0171] Metallic components of the active-matenal-containing accumulator components, for example nickel or cobalt, which are present in ionic form and usually as components of salts, form metal-hexammine complexes (M(NHs)6, M: metal, here: nickel or cobalt) that are dissolved in the leaching solution 16. The leaching solution enriched with the metal-hexammine complexes is called pregnant leaching solution 20.

[0172] The leaching reactor has an optional solid-liquid separator 21 for separating the pregnant leaching solution 20 from the leached accumulator components. For example, the solid-liquid separator 21 comprises a sieve, for example with a mesh size of less than 5 pm (and preferably at least 1 pm).

[0173] The pregnant leaching solution 20 is conveyed to an optional copper separator 24 via a leaching solution discharge line 22. For example, the copper separator 24 has two electrodes 25.1, 25.2, between which a voltage U22 is applied, which is chosen to be high enough that Cu 2+ -ions are deposited as metallic copper 26. Alternatively, the copper separator 24 can be configured to allow the addition of a substance that degrades the Cu 2+ -ions are reduced and thereby oxidized and go into solution.

[0174] The pregnant leaching solution 20 is fed into a precipitation generator 27 via the leaching solution discharge line 22. The precipitation generator 27 is designed to treat the pregnant leaching solution 20 so that a precipitate 32 forms. In this case, the precipitation generator 27 includes an ammonia injection device 28. Ammonia 30, which is preferably in gaseous form, is introduced into the pregnant leaching solution 20 by means of the ammonia injection device 28. A pressure p28, which is, for example, ambient pressure, prevails in the ammonia injection device 28. This causes a precipitate 32 to form, which can also be referred to as a precipitate. The precipitate contains, for example, at least one sulfate of the metallic component M.

[0175] Alternatively or additionally, the precipitation generator 27 can have a cooling system 29. For example, the cooling system 29 is configured to reduce the temperature of the leaching solution T27 in the precipitation generator 27 by at least 10 Kelvin, preferably at least 20 Kelvin, and particularly preferably at least 30 Kelvin.

[0176] By means of a precipitation separator 34, which can be arranged in the ammonia injection device 28, on the ammonia injection device 28 or spatially separated from the ammonia injection device 28, the precipitation 32, for example Mx(NH3)eSO4 or M x (NH3)eCO3 is separated. For example, the precipitation separator 34 includes a sieve and / or a centrifuge.

[0177] By separating the precipitate 32, the pregnant leaching solution 20 becomes depleted leaching solution 38. In other words, in the material flow direction R of the leaching solution downstream of the precipitate separator 34, the solution is referred to as depleted leaching solution 38.

[0178] The depleted leaching solution 38 still contains the ammonium compound NH4X (here: (NF ^SCU)) as well as dissolved ammonia. For example, the concentration of dissolved ammonia is 15 to 30 wt%.

[0179] The depleted leaching solution 38 is supplied to a regenerator 41 via a line 40, which produces leaching solution 16 from the depleted leaching solution 38, which can be used again for leaching accumulator components 12. i.

[0180] In the present case, the regenerator 41 comprises an ammonia removal device 42, which removes at least some, and in particular predominantly, of the ammonia. For this purpose, the ammonia removal device 42 reduces the pressure to, for example, P42 < P28. For example, P42 < P28 - 10 bar. Alternatively or additionally, the temperature of the depleted leaching solution 38 in the regenerator 41 is increased by a heater 43 of the regenerator 41, for example, by at least 5 Kelvin, and in particular by at least 10 Kelvin. Alternatively again, an inert gas 44 is introduced into the depleted leaching solution 38, which accelerates the removal of the ammonia 30.

[0181] If inert gas 44 is used, it is separated by a gas separator 46 and recirculated. The ammonia 30 is compressed by means of a compressor 48. A gas dryer 50 can be arranged upstream or downstream of the compressor to dry the ammonia 30. The compressed, optionally solidified, ammonia enters an ammonia storage tank 52. From the ammonia storage tank 52, it can be reintroduced into the pregnant leaching solution 20 via the ammonia injection device.

[0182] The removal of ammonia produces regenerated leaching solution 54, which is returned to the leaching reactor 14 via a return line 55. However, it is not necessary to use this regenerated leaching solution 54 to leach the accumulator components 12 i that have already been leached. It is also possible to leach other accumulator components.

[0183] In the material flow direction R of the generated leaching solution 54 downstream of the ammonia expulsion device 42, an optional feeder 56 of the regenerator 41 is arranged, which is configured to add a substance containing or forming ammonium ions and / or a substance containing or forming the anion X, for example a compound NH4X, to the regenerated leaching solution 54. In the formula NH4X, X is an anion, for example a halide ion, a chalcogenide ion, or an SO4 ion. 2 '-lon or a CO3 2 '-lon.

[0184] Preferably, the dosing unit 56 is configured for automatically measuring the ammonium salt concentration, for example by means of a concentration sensor 58, and for automatically dosing the ammonium compound so that a predetermined target ammonium compound concentration is established. The concentration sensor 58 measures the concentration of the ammonium compound, for example by measuring its electrical conductivity.

[0185] The recycling plant 10 can include a first scrubber 60.1, which can also be referred to as a conducting salt solvent scrubber. The first scrubber 60.1 is configured to wash accumulator components 12, in particular in the form of black mass 62, with a washing solvent 64.1, such that conducting salt solvent 66 of a conducting salt of the accumulator, from which the accumulator components 12 were produced, is removed. Accumulator components washed by the scrubber 60.1, in particular black mass 62, can be fed directly to the leaching reactor 14. The first scrubber 60.1 can also be configured to wash out conducting salt and conducting salt solvent.

[0186] Alternatively or additionally, the recycling plant 10 can have a second scrubber 60.2, which can also be referred to as a conducting salt scrubber. The second scrubber 60.2 is designed for washing accumulator components 12, for example in the form of black mass 62, with washing solvent 60.2, so that conducting salt 68 of the accumulator is removed. It is advantageous if, as shown in Figure 1, the scrubbers 60.1, 16.2 are arranged one after the other and first conducting salt solvent 66 and then conducting salt 68 are washed out.

[0187] The first washing solvent 64.1 is, for example, EMC or DMC. The second washing solvent 64.2 is, for example, ethanol.

[0188] Alternatively or additionally, the recycling plant 10 can have a third scrubber 60.3, which can also be referred to as a binder scrubber. The third scrubber 60.3 is designed for washing accumulator components 12, for example in the form of black mass 62, with a binder solvent for dissolving the binder. The binder solvent is, for example, DMSO.

[0189] It should be noted that recycling plant 10 may have one, two or three washers.

[0190] The recycling plant 10 can include a shredding unit 70 for shredding, preferably fully discharged, accumulators 72.j (j = 1, 2, ... ), so that shredded material 74 is produced. The shredded material 74 is fed to an optional dryer 76, where, preferably at a temperature below 50 °C and at a pressure below 100 hPa, conducting salt solvent is removed by evaporation.

[0191] The dried shredded material 74' is fed to an optional separating device 78. The separating device 78 separates the black mass from housing parts, metal parts, and separator films. For this purpose, the separating device 78 comprises, for example, a magnetic separator and / or a classifier, in particular a cross-flow classifier and / or a zigzag classifier. In this way, black mass 62 is produced. It is also possible for the separating device 78 to be arranged downstream of the binder washer in the material flow direction.

[0192] Recycling plant 10 can at least produce a first lye container.

[0193] 108.1, which is designed to receive leaching solution, for example, pregnant, depleted, or regenerated leaching solution. The leaching reactor 14 can, in particular, be operated in batch mode.

[0194] Recycling plant 10 can accommodate at least one second lye container.

[0195] 108.2, which is designed to receive leaching solution, for example, pregnant, depleted, or regenerated leaching solution. The second leaching container preferably contains an leaching solution of a different chemical composition than the first leaching solution of 108.1. In this way, it is possible to operate the leaching reactor 14 with different leaching solutions.

[0196] Accumulator components 12 leached by leaching in the leaching reactor 14, in this case leached black mass 80, can be further processed according to an embodiment as shown in Figure 2a.

[0197] The components of the recycling plant 10, surrounded by a dashed line, form a regeneration plant 83.

[0198] The regeneration unit 83 can include a lithium extractor 85 for removing lithium from the pregnant leaching solution 20. The lithium extractor is arranged upstream of the ammonia injection device 28. The pregnant leaching solution 20 flows past an ion exchange material 118, which is selective for lithium, thereby releasing lithium ions to the ion exchange material 118. The ion exchange material 118 can be regenerated in a downstream regenerator 124 (see Figure 6).

[0199] Figure 2a shows that the recycling plant 10 can have an optional binder scrubber 82 in which the leached black mass 80 is washed by means of a binder solvent 84, so that binder 86 is removed. This results in low-binder or binder-free black mass 80'. Alternatively or additionally, the recycling plant 10 can have a black mass cleaner 88 in which leached, in particular low-binder or binder-free, black mass 80' is mixed with volatile acid 90, for example, formic acid, so that aluminum and / or manganese and / or copper pass into a solution 92 and are drawn off. After removal of the volatile acid by evaporation, graphite 94 is obtained.

[0200] Figure 2b shows that the precipitate 32 (see Figure 1) can be heated in an oven 96 to produce a nickel-cobalt salt Ni x Co y to obtain Y with an anion Y. For example, for the anion Y = SO4 2CO3 2 ; OH halide ion. Other anions are possible.

[0201] In an optional mixing reactor 98 of the recycling plant 10, the nickel-cobalt salt Ni x Co y Y an aqueous solution 99 containing manganese ions, for example a sulfuric acid MnSO4 solution, is added. Subsequently, impurities are removed, for example by means of an ion chromatography instrument 100. A base 104, for example NaOH, can then be added to the purified solution in a vessel 102. This yields a cathode-active material precursor 106, which is preferably used for the production of new accumulators.

[0202] Figure 3 shows a fourth embodiment of a recycling plant 10 according to the invention, in which the accumulator components 12 are leached at a leaching temperature of T14 = 150 °C. The pressure pu is chosen to be high enough that the lye does not boil. The leached accumulator components 80 can be heated to a phase transition temperature Tpu in an optional oven 110, but this is not necessary. If they are heated, the phase transition temperature Tpu is chosen such that NMC components in the accumulator components undergo a phase change to at least 30% by weight, preferably at least 40% by weight, and particularly preferably at least 50% by weight. For example, the phase transition temperature is at least Tpu = 200 °C and / or at most Tpu = 350 °C.

[0203] The accumulator components 80 treated in this way are then leached in a second leaching reactor 14'. It is possible, but not necessary, for the second leaching reactor to contain a second leaching solution 16' that differs from the first leaching solution 16. The second leaching reactor 14 can be part of a second plant unit 112.2, which is constructed in the same way as the first plant unit 112.1 described above. Both plant units 112.1 and 112.2 constitute the recycling plant 10. The components of the second plant unit 112.2 are indicated by an apostrophe.

[0204] It is also possible that the leached accumulator components, heated to phase transition temperature, are leached again in the same reactor 16. It is possible that a second leaching solution is used for this purpose, which differs from the first leaching solution used initially.

[0205] Figure 4 shows a further embodiment of a recycling plant 10 according to the invention, in which the copper separator 24 comprises the electrolysis unit 24a and additionally a cementation unit 24b. Copper is first electrolytically deposited from the pregnant leaching solution 20 by the electrolysis unit 24. The copper-depleted solution thus obtained enters the cementation unit 24b, which is designed as a thin tube and contains nickel powder 23. In this way, a solution is obtained that contains hardly any copper. This solution is then fed to the ammonia injection device 28.

[0206] Figure 4 also shows that the feeder 56 can be configured to feed in a sulfate ion-forming agent 112, for example in the form of sulfuric acid. The reaction of the sulfate ion-forming agent 112 with the regenerated leaching solution 54 generates heat of reaction, which raises the temperature of the leaching solution 54 to a desired leaching temperature T. The leaching temperature Ti 6 is set by means of an optional, for example electrically operated, leaching solution temperature control unit 114.

[0207] Figure 5 shows a further embodiment of a recycling plant 10 according to the invention, in which the regenerator 41 comprises a lithium remover 45, in particular a lithium salt remover. Depleted leaching solution 38, in particular leaching solution from the ammonia removal device 42, is supplied to the lithium remover 45 and reduces the concentration of lithium compounds. For example, the lithium remover 45 is designed as an evaporator that evaporates the water and optionally ammonia in the leaching solution, leaving a lithium-containing residue 114. The evaporated water is condensed and optionally mixed with leaching solution not supplied to the lithium remover 45, which comes from the ammonia removal device 42.

[0208] If necessary, the correct concentration of the ammonium compound NH4X is then adjusted. The lithium remover 45 can be used independently of the other components of the recycling plant 10 in other embodiments.

[0209] Figure 6 shows a recycling plant 10 according to a seventh embodiment of the invention. Accumulator components 12, in particular black mass 62, are fed into the leaching reactor 14. The devices located upstream in the material flow direction R' are optional.

[0210] The regeneration unit 83 has an ion exchange unit 116, which is configured to bring the pregnant leaching solution 20 into contact with a first ion exchange material 118, which in the present embodiment is in the form of granules with a plurality of particles 12O.k (k = 1, 2, ... ). The pregnant leaching solution 20 flows through a first ion exchanger 122, in which the first ion exchange material 118 is arranged, selectively binding lithium from the pregnant leaching solution 20. This results in selectively depleted leaching solution 123.

[0211] The first ion exchange material 118 can be regenerated using a first regenerator 124. For this purpose, the ion exchange material 118 from the first ion exchanger 122 can be introduced into the first regenerator 124, where it is brought into contact with a first acid 126, for example, formic acid, hydrochloric acid, or sulfuric acid. The lithium ions bound by the first ion exchange material 118 are thereby released and replaced by protons. The resulting solution is neutralized, for example, with a base, so that a lithium salt is formed.

[0212] The selectively depleted leaching solution can be fed to an optional copper separator 24.

[0213] The regeneration unit 83 can have a second ion exchange unit 127, which is arranged downstream of the first ion exchanger 122, optionally downstream of the copper separator 24, in the material flow direction R of the leaching solution. The second ion exchange unit 127 has a second ion exchanger 128, which contains a second ion exchange material 130, which in turn can be in the form of particles 132. The second ion exchange material 130 selectively removes at least one metallic component that has not already been removed in the first ion exchanger 122. In the present case, the second ion exchange material selectively binds to nickel, cobalt, and manganese ions.

[0214] The second ion exchange material can be generated using a second regenerator 134. For this purpose, the second ion exchange material 130 is brought into contact with a second acid 136. The second acid 136 can be the same as the first acid.

[0215] Optionally, the regeneration system has a cleaning device 138 for purifying the resulting leaching solution. The cleaning device 138 has, for example, an ion exchanger which is more selective for interfering metals, such as heavy metals, especially cadmium or mercury. Alternatively or additionally, the cleaning device 138 is designed to remove

[0216] Fluoride, for example by precipitation with a calcium compound.

[0217] Reference symbol list

[0218] 10 recycling plants, 56 feeders

[0219] 12 Accumulator component 58 Concentration sensor

[0220] 14 leaching reactor 60 scrubbers

[0221] 16 leaching solution 62 black mass

[0222] 18 stirrers 64 washing solvents

[0223] 20 pregnant leaching solution 66 conducting salt solvent

[0224] 21 Solid-liquid separator 68 Conductive salt

[0225] 22 Lye solution discharge line 69 Binder

[0226] 23 nickel powder 70 grinding unit

[0227] 24 copper separators 72 accumulators

[0228] 24a Electrolysis unit 74 Material to be ground

[0229] 24b Cementation Unit 76 Dryer

[0230] 25 Electrode 78 Disconnecting device

[0231] 26 metallic copper 80 leached accumulator stock¬

[0232] 27 precipitation-producing parts, leached black mass

[0233] 28 Ammonia injection device 82 Binder scrubber

[0234] 29 Cooling 83 Regeneration system

[0235] 30 Ammonia 84 Binder solvents

[0236] 32°C precipitation, 86°C binder

[0237] 34 Precipitation separators 88 Black mass cleaners

[0238] 38 depleted lye solution 90 acid

[0239] 40 Line 92 Solution

[0240] 41 Regenerator 94 Graphit

[0241] 42 Ammonia ejection device 96 Oven

[0242] 43 Heating 98 Mixing reactor

[0243] 44 Inert gas 99 aqueous solution

[0244] 45 Lithium remover 100 ion chromatography instrument

[0245] 46 gas separators 102 vessels

[0246] 48 Compressor 104 Base

[0247] 50 gas dryers 106 cathode active material precursor

[0248] 52 ammonia storage containers, 108 lye containers

[0249] 54 regenerated leaching solution 110 furnace

[0250] 55 Return line 112 Sulfate ionizer, sulfuric acid 114 Lye solution temperature control

[0251] 116 ion exchange unit

[0252] 118 ion exchange material

[0253] 120 particles

[0254] 122 first ion exchanger

[0255] 123 selectively depleted leaching solution

[0256] 124 first regenerator

[0257] 126 first acid

[0258] 127 second ion exchange unit

[0259] 128 second ion exchanger

[0260] 130 second ion exchange material

[0261] 132 particles

[0262] 134 second regenerator

[0263] 136 second acid i Running index (accumulator components) j Running index (accumulators) k Running index (particles)

[0264] M metallic component n running index (leaching)

[0265] N Number of leaching operations pi4 Pressure in the leaching reactor

[0266] P28 Pressure in the ammonia-

[0267] insertion device

[0268] P42 Pressure in the ammonia ejection device

[0269] R Material flow direction

[0270] T14 leaching temperature in

[0271] leaching reactor

[0272] T27 Leaching solution temperature in the precipitation generator

[0273] U22 voltage

Claims

Patent claims 1. Method for recycling active material-containing accumulator components (12) from accumulators (72), in particular black mass (62), comprising the steps: (a) Lying the accumulator components (12), in particular the black mass (62), with lye solution (16), which (i) Ammonia (30) and (ii) contains at least one ammonium compound (Nh X), in particular an ammonium salt, such that at least one metallic component (M) passes at least partially from the accumulator components (12), in particular the black mass (62), into the leaching solution (16), thus forming a pregnant leaching solution (20) containing at least one metal-hexammine complex (M(NHS)6, M: metal), and (b) Regenerating the pregnant leaching solution by removing at least one metallic component (M) from the pregnant leaching solution (20), in particular from the metal-hexammine complex (M(NHs)6), so that regenerated leaching solution (54) is obtained.

2. The method according to claim 1, characterized in that the regeneration of the pregnant leaching solution comprises the following steps: (i) Introducing ammonia, in particular gaseous ammonia (30), into the pregnant leaching solution (20), and / or Cooling the pregnant leaching solution (20) so that a precipitate (32) forms, (ii) Separating the precipitate (32) from the leaching solution, so that depleted leaching solution (38) is obtained, and (iii) Reducing the ammonia concentration in the depleted leaching solution (38), in particular driving off ammonia (30) from the depleted leaching solution (38) so that regenerated leaching solution (54) is obtained.

3. Method according to claim 2, characterized in that the introduction of the ammonia (30) into the pregnant leaching solution (20) is carried out in such a way that the precipitate (32) is formed by displacement crystallization.

4. A method according to any of the preceding claims, characterized in that the regeneration of the pregnant leaching solution comprises the following steps: (i) Contacting the pregnant leaching solution (20) with an ion exchange material for the selective removal of a metallic component, in particular lithium, from the pregnant leaching solution (20) to obtain selectively depleted leaching solution, (ii) Separation of selectively depleted leaching solution and ion exchange material and (iii) Regenerating the ion exchange material to obtain a compound of the metallic component and regenerated ion exchange material.

5. Method according to one of the preceding claims, characterized in that the regeneration of the leaching solution comprises the following step: removal of copper from the pregnant leaching solution and / or the selectively depleted leaching solution, in particular by electrolysis or cementation.

6. Method according to one of the preceding claims, characterized in that the regeneration of the leaching solution comprises the following step: (i) Contacting the selectively depleted leaching solution with a second ion exchange material for the selective removal of at least one second metallic component, in particular nickel, cobalt and / or manganese, from the selectively depleted leaching solution so that the regenerated leaching solution is obtained, (ii) Separating the leaching solution thus obtained and the second ion exchange material and (iii) Regenerating the second ion exchange material to obtain a compound of the at least one second metallic component and regenerated second ion exchange material.

7. Method according to one of the preceding claims, characterized by the steps (a) Comminuting at least one accumulator (72.1 , 72.2), in particular an alkaline accumulator, so that comminution material (74) is produced, and (b) Separation of black mass (62) from the material to be crushed (74).

8. Method according to one of the preceding claims, characterized by the step: (a) optionally adding ammonium salt (NH4X) to the, in particular regenerated, leaching solution (54) and (b) reusing the regenerated leaching solution (54) to leach accumulator components (12), in particular black mass (62).

9. Method according to one of the preceding claims, characterized in that the leaching of the active material-containing accumulator components (12) with leaching solution (16) (a) at a temperature (T14) of at least 10 °C and / or at most 300 °C and / or (b) at a pressure (pu) of at least 6 bar and / or at most 35 bar.

10. Method according to one of the preceding claims, characterized by the step prior to leaching the black mass (62) (a) Washing the active material-containing accumulator components (12), in particular the black mass (62), with a washing solvent (60.1 ), so that conducting salt solvent (66) of a conducting salt (68) of the accumulator is removed and / or (b) Washing the active material-containing accumulator components (12), in particular the black mass (62), with a washing solvent (60.2), so that conducting salt (68) of the accumulator is removed and / or (c) Washing the active material-containing accumulator components (12), in particular the black mass (62), with a binder solvent (84) so ​​that binder (86) of the accumulator is removed and / or (d) Drying the material to be crushed, especially after washing.

11. Method according to one of the preceding claims, characterized by the steps (a) after leaching the accumulator components (12) so that leached accumulator components (12) are formed, re-leaching the leached accumulator components (12) with primary leaching solution (16) which, after the removal of the ammonia (30), has not yet been used to leach accumulator components (12) or which has never been used for leaching, and / or (b) Lying of unleached accumulator components (12) with pregnant lye solution (20).

12. Method according to claim 11, characterized by the steps of at least three leaching of the accumulator components (12), in particular the black mass (62), wherein the accumulator components (12), in particular the black mass (62), which has been leached most frequently, is leached with leaching solution (16) with which no black mass (62) has yet been leached.

13. Method according to one of the preceding claims, characterized by the step Deposition of copper (26) from the pregnant leaching solution (20), in particular by electrolysis or cementation.

14. Method according to one of the preceding claims, characterized by the steps (a) Dissolving binder (86) from the leached black mass using a binder solvent (84) and / or (b) Extraction of manganese and / or aluminium and / or copper components from the leached black mass using a volatile acid (90).

15. Method according to one of the preceding claims, characterized by the steps (a) Heating the precipitate to form a nickel-cobalt salt (Ni x Co y Y) forms (b) Adding a manganese compound, in particular a manganese salt, preferably MnSCU, (c) Removal of metallic impurities, in particular by means of ion chromatography, (d) Adding a base, in particular an alkali metal hydroxide, so that a cathode material precursor precipitates.

16. Recycling plant for the recycling of active material-containing accumulator components (12) of accumulators (72), in particular of shredded material (74) of accumulators (72), with (a) a leaching reactor (14) which (i) is designed to alkalize the accumulator components (12), in particular the black mass (62), and (ii) leaching solution (16) contains which ammonia (30) and at least one ammonium compound (Nh X), in particular an ammonium salt (Nh X), such that pregnant leaching solution (20) is formed during leaching, (b) a regeneration unit (83) configured to regenerate the leaching solution by removing at least one metallic component (M) from the pregnant leaching solution, in particular from the metal hexammine complex (M(NHs)6), such that regenerated leaching solution (54) is obtained.

17. Recycling plant for recycling according to claim 16, characterized in that the regeneration plant (83) (i) a precipitate generator (27) configured to treat the pregnant leaching solution (20) so that a precipitate (32) is formed, in particular an ammonia injection device (28) configured to introduce, in particular gaseous, ammonia (30) into the pregnant leaching solution (20), (ii) a precipitation separator (34) for separating the precipitation (32) so that depleted leaching solution (38) is obtained, and (iii) comprises a regenerator (41) for producing regenerated leaching solution (16) from the depleted leaching solution (38).

18. Recycling plant according to claim 16 or 17, characterized in that the regenerator (41 ) has an ammonia drive-off device (42) which is designed to drive off ammonia (30) from the depleted leaching solution (38) so that regenerated leaching solution (54) is produced.

19. Recycling plant according to one of claims 16 to 18, characterized by (a) a comminution unit (70) for comminution of accumulators (70) and / or (b) a separating device (78) for separating black mass (62) from the material to be crushed (74) and / or (c) a feeder (56) designed to add ammonium salt (NH4X) to the, in particular regenerated, leaching solution (54) and / or (d) a scrubber (60.1) arranged for washing the black mass (62) with a washing solvent (64.1) such that conducting salt solvent (66) of a conducting salt (68) of the accumulator (72) and / or conducting salt (68) is removed, and / or (e) a copper separator (24) arranged to separate copper (26) from the pregnant leaching solution (20).

20. Recycling plant according to one of claims 16 to 19, characterized in that the regeneration plant (83) (a) has a first ion exchange unit (116) configured to (i) Contacting the pregnant leaching solution (20) with an ion exchange material for the selective removal of a metallic component, in particular lithium, from the pregnant leaching solution (20) to obtain selectively depleted leaching solution, (ii) Separation of selectively depleted leaching solution and ion exchange material and (iii) Regenerating the ion exchange material to obtain a compound of the metallic component and regenerated ion exchange material. (b) has a second ion exchange unit (127) configured to (i) Contacting the selectively depleted leaching solution with a second ion exchange material for the selective removal of at least one second metallic component, in particular nickel, cobalt and / or manganese, from the selectively depleted leaching solution, so that the regenerated leaching solution is produced, (ii) Separating the leaching solution thus obtained and the second ion exchange material and (iii) Regenerating the second ion exchange material to obtain a compound of at least one second metallic component and regenerated second ion exchange material.

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