Method for obtaining lithium salts from black mass

Abstract

The present invention relates to a method for obtaining lithium salts from black mass from the mechanical recycling of lithium batteries, in particular from lithium-ion secondary batteries, comprising the following steps: i) providing a sulphuric-acid-containing aqueous solution of lithium peroxodisulphate by electrolysis of an aqueous solution of lithium sulphate in a divided electrolysis cell, wherein a sulphuric-acid-containing aqueous solution of lithium peroxodisulphate and oxygen is obtained in the anode chamber of the divided electrolysis cell and an aqueous lithium hydroxide solution and hydrogen are obtained in the cathode chamber of the divided electrolysis cell; ii) treating the black mass with the sulphuric-acid-containing aqueous solution of lithium peroxodisulphate provided in step i), wherein a first aqueous solution is obtained which contains the lithium contained in the black mass in the form of the sulphates and / or phosphates thereof and at least some of the polyvalent metals contained in the black mass in the form of the sulphates and / or phosphates thereof; iii) depleting the polyvalent metals and the optionally contained phosphate from the first aqueous solution to obtain a second aqueous solution which is depleted of polyvalent metals and optionally of phosphate and contains lithium in the form of a dissolved salt and sulphate; iv) obtaining the lithium in the form of a salt from the second aqueous solution and / or from the aqueous lithium hydroxide solution obtained in the cathode chamber.

Description

[0001] Method for extracting lithium salts from black mass

[0002] The invention relates to a method for obtaining lithium salts from black mass obtained by recycling lithium batteries.

[0003] As electrification increases in many areas, such as electromobility, solar power storage and electronics, lithium batteries, especially Li-ion accumulators, hereinafter also referred to as Li-secondary batteries, play an increasingly important role.

[0004] To increase the environmental compatibility and economic viability of this technology, various concepts such as "second life," repair, remanufacturing, and refurbishment are being pursued to extend the service life of lithium-ion batteries. However, to improve sustainability, conserve the sometimes limited availability of raw materials—primarily graphite and valuable transition metals such as cobalt, nickel, manganese, and copper, in addition to lithium—and address the increasing dependence on third-party countries for these resources, it is essential to recover these raw materials from used and no longer functional lithium-ion batteries. Furthermore, in addition to manufacturers taking back lithium batteries, the recycling of non-functional primary and secondary lithium batteries is legally mandated in many countries.

[0005] The processes for reprocessing lithium-ion batteries can be broadly divided into the following three areas:

[0006] 1) Mechanical processes

[0007] 2) Pyrometallurgical processes

[0008] 3) Hydrometallurgical processes

[0009] Overviews of these processes and their combinations in the recycling of primary and secondary lithium batteries can be found in V. Marcinov et al., Metals 2023, 13, 1213; and in HH Heimes et al. in Elektromobilität (eds.: A. Kampker, HH Heimes), Springer, Berlin, Heidelberg, 2024, Chapter 43, pp. 687-704. The mechanical processes are based on shredding lithium cells after battery disassembly and subsequently separating the components based on physical parameters such as density. The most important valuable material obtained is the so-called black mass, which essentially contains the metals in the lithium cells and conductor layers in the form of salts and / or oxides, as well as the carbon electrode material. The mechanical processes often serve as a pretreatment or pre-sorting step before one of the other two processes is used, in which the black mass is broken down.

[0010] Pyrometallurgical processes are based on the thermal treatment of the black mass obtained during mechanical processing. In this process, the carbon typically used as electrode material in lithium batteries is burned, and the metallic components are combined to form a slag or ash. This residue is then used in conventional manufacturing processes for materials such as copper, nickel, manganese, and cobalt from primary ores.

[0011] Hydrometallurgical processes are based on treating the black mass with acids or oxidative digestion reagents such as H₂O₂. In this process, the black mass is digested with large quantities of reagent to dissolve the metals. Subsequently, metal salts are separated, washed, and, depending on their purity, returned to the cycle by utilizing pH shifts, precipitation reactions, and solid-liquid separations.

[0012] The disadvantages of known hydrometallurgical processes can be summarized as follows:

[0013] Handling large quantities of chemicals such as acids, alkalis, oxidizing and precipitating agents;

[0014] Stockpiling of peroxides with the associated safety requirements; low space-time yields and therefore high equipment costs;

[0015] Large quantities of wastewater and sludge.

[0016] The disadvantages of pyrometallurgical processes can be summarized as follows: use of large quantities of fuel and / or electrical energy;

[0017] The need for complex exhaust gas purification processes;

[0018] Lithium is bound in the slag and can only be extracted from it with great effort; the critical raw material graphite serves as an energy carrier and cannot be recycled.

[0019] All technologies for extracting black mass from the mechanical recycling of lithium batteries use chemicals on a stoichiometric scale. These result in immense resource consumption and waste during production and subsequent disposal. Furthermore, the energy input required for pyrolysis is high. These methods alone will not be sufficient to achieve the recycling rates required in the future.

[0020] CN 116902998 describes the extraction of lithium from lithium iron phosphate, comprising the treatment of lithium iron phosphate with aqueous ammonium peroxodisulfate to extract the lithium, followed by the removal of impurities by treatment with ion exchange resins, and subsequent electrodialysis of the treated extract across a bipolar membrane to obtain an aqueous sulfuric acid solution and an ammoniacal lithium hydroxide solution. This solution must be deaminated using a membrane before the lithium hydroxide can be crystallized. This process requires the complex disassembly of batteries into individual components to selectively obtain the lithium phosphate electrode material. Furthermore, it cannot be applied to the treatment of black mass, as the process uses pure lithium iron phosphate without graphite.

[0021] CN 116119637 describes the treatment of lithium iron phosphate with an oxidizing agent in the anode compartment of a split electrolysis cell. This process dissolves the lithium from the lithium iron phosphate, which then migrates through the cell membrane into the cathode compartment, where it accumulates in the catholyte. Sodium peroxodisulfate is primarily used as the oxidizing agent. During treatment, it is reduced to sulfate and regenerated to persulfate through the anode reaction. This process also requires the complex disassembly of the batteries into their individual components and focuses exclusively on the extraction of lithium from lithium iron phosphate. The conditions are chosen to prevent other metals from dissolving as much as possible. This is achieved primarily by maintaining a pH of 7. A direct comparison with black mass is not possible here, as all metals must be separated from the graphite.

[0022] US 2019 / 207275 describes the treatment of electrode material from lithium batteries, specifically lithium iron phosphate previously separated from the battery, with an aqueous solution of lithium peroxodisulfate. Lithium peroxodisulfate is obtained by reacting lithium hydroxide with ammonium peroxodisulfate as an ammoniacal aqueous solution. The extraction is carried out without strong acids to ensure minimal leaching of the iron, which is obtained as iron phosphate. This method is unsuitable for recovering the transition metals contained in black mass. Furthermore, this method also requires the complex disassembly of the batteries into their individual components to selectively obtain the lithium phosphate electrode material. The replacement of ammonium ions with Li + It also requires a high level of equipment and generates by-products of chemicals that need to be disposed of.

[0023] The invention is therefore based on the objective of providing a simple, efficient method for recovering lithium salts from black mass in the mechanical recycling of lithium batteries, which at least partially overcomes the disadvantages of the prior art. In particular, the method should not require stoichiometric or superstoichiometric amounts of chemicals, such as acids and precipitating agents, in order to avoid large quantities of waste. Furthermore, the energy input required to carry out the method should be as low as possible and essentially limited to the use of electricity, so that primarily renewable energy sources can be used. In addition, the method should allow the recovery of one or more of the transition metals contained in the black mass and, optionally, the phosphate contained in the black mass.

[0024] It was found that these and other problems can be solved by the process described here and below, in which the black mass from the mechanical recycling of lithium batteries, especially lithium-ion accumulators, is treated with a sulfuric acid aqueous solution of lithium peroxodisulfate. This solution is first provided by electrolysis of an aqueous solution of lithium sulfate in a split electrolysis cell. This yields an initial aqueous solution containing the lithium present in the black mass in the form of sulfates and / or phosphates, as well as at least some of the polyvalent metals present in the black mass in the form of their sulfates and / or phosphates. From this solution, the transition metals, aluminum, and lithium, as well as any phosphate present, can then be recovered.A key aspect of the invention is the use of lithium in the electrochemical in-situ production of peroxodisulfate for the digestion of the black mass. The lithium hydroxide or the lithium carbonate obtained from it, which is formed in the catholyte, can be used to precipitate other accompanying metals. Lithium can thus be recycled, avoiding the external addition of chemicals and allowing net lithium removal from the process. Furthermore, no alkali metal impurities are introduced, eliminating the need for complex subsequent purification.

[0025] Accordingly, the present invention relates to a method for obtaining lithium salts from black mass from the mechanical recycling of lithium batteries, in particular from lithium-ion secondary batteries, comprising the following steps: i) providing an aqueous sulfuric acid solution of lithium peroxodisulfate by electrolysis of an aqueous solution of lithium sulfate in a divided electrolysis cell, wherein an aqueous sulfuric acid solution of lithium peroxodisulfate and oxygen is obtained in the anode compartment of the divided electrolysis cell, and an aqueous lithium hydroxide solution and hydrogen are obtained in the cathode compartment of the divided electrolysis cell;ii) Treatment of the black mass with the aqueous sulfuric acid solution of lithium peroxodisulfate provided in step i), yielding a first aqueous solution containing the lithium present in the black mass in the form of its sulfates and / or phosphates, as well as at least some of the polyvalent metals present in the black mass in the form of their sulfates and / or phosphates; iii) Removal of the polyvalent metals and any phosphate present from the first aqueous solution to obtain a second aqueous solution, depleted of polyvalent metals and any phosphate, containing lithium in the form of a dissolved salt and sulfate; iv) Recovery of the lithium in the form of a salt from the second aqueous solution and / or from the aqueous lithium hydroxide solution obtained in the cathode compartment.

[0026] This process offers several advantages. Unlike conventional hydrometallurgical processes, it does not require stoichiometric or superstoichiometric amounts of reagents. Instead, the lithium sulfate required can be directly produced from the lithium salt obtained from the black mass by reacting it with sulfuric acid or sulfate from the peroxodisulfate digestion, and then recycled back into the process. The lithium hydroxide produced during electrolysis in the catholyte can be easily isolated either by precipitation with CO₂ as lithium carbonate or by cooling the solution to obtain solid lithium hydroxide. This solid is characterized by high purity, as only lithium-containing starting materials need to be used. The resulting lithium carbonate can therefore be used directly for the production of lithium batteries.

[0027] Furthermore, the alkaline catholyte can be partially used to precipitate the transition metal and aluminum salts dissolved during the treatment of the black mass in step ii). This allows the use of additional reagents to be essentially limited to the initially used lithium sulfate or sulfuric acid, and drastically reduces the waste load compared to known hydrometallurgical processes. In addition, the transition metal salts dissolved during the treatment of the black mass in step ii) can be easily separated and recovered. The second aqueous solution obtained in step iii), depleted of aluminum and transition metals, can be at least partially recycled to the anode compartment and used there to produce lithium peroxodisulfate and thus digest the black mass. This further reduces the reagent requirement.Compared to other hydrometallurgical processes, the process according to the invention allows for higher space-time yields. Furthermore, hydrogen is produced during electrolysis, which can be used for reconversion into electricity and therefore contributes advantageously to the energy balance of the process.

[0028] Unlike the prior art processes for the reprocessing of lithium iron phosphate, the treatment of the black mass does not take place in the electrolysis cell itself, but in a separate reaction vessel. This allows for better control of peroxide formation in step i). Furthermore, it has been shown that the analogous application of the prior art processes to black mass is problematic, since with the increasing dissolution of aluminum and transition metal salts in the anolyte, these elements interfere with the actual oxidation reaction and also reduce the lifetime of the cation exchange membrane.

[0029] Furthermore, the separate execution of steps i) and ii) leads to an increased yield of lithium and other metals in the treatment of the black mass in step ii), relative to the metals contained in the black mass. In addition, the separate execution of steps i) and ii) enables the use of flow cells, whose power and energy efficiency, and thus the space-time yield, is higher than that of the pot cells used in the prior art in step i).

[0030] According to the invention, the process in step i) comprises the provision of an aqueous solution of lithium peroxodisulfate by electrolysis of an aqueous solution of lithium sulfate. The partial and overall reactions taking place here can be described by the following reaction equations (1a)-(1c):

[0031] Anode reaction: Li2SO41 / 2 Li2S2O8+ Li + + e“ (la)

[0032] Cathode reaction: H2O + e“ — ► OH“ + 1 / 2 H2(lb)

[0033] Gross reaction: Li2SO4+ H2O 1 / 2 Li2S2O8+ LiOH + 1 / 2 H2(lc)

[0034] The electrolysis is carried out in a divided electrolysis cell, i.e., the anode and cathode compartments are spatially separated by a separator, e.g., by a membrane or a diaphragm, in particular by a cation-selective membrane, e.g., a cation-selective ceramic membrane or a cation exchange membrane. Cation exchange membranes, e.g., cation exchange membranes from Nation, are particularly preferred.

[0035] In the anode compartment, lithium peroxodisulfate is formed through the electrochemical oxidation of lithium sulfate. Oxygen is produced as a side reaction. In the cathode compartment, hydrogen and hydroxide ions are formed. Electroneutrality in the cathode compartment is ensured by the transport of lithium ions from the anode compartment to the cathode compartment through the separator. This transport allows the lithium to be separated from any other metal salts that may be present in the solution.

[0036] In principle, all materials exhibiting high acid stability are suitable as anode materials. Examples include platinum, dimensionally stable anodes (e.g., ir- and / or rub-oxide on titanium or tantalum), lead dioxide, tin oxide, graphite, glassy carbon, carbon composites, and boron-doped diamond. Preferably, the anode material of the split electrolysis cell comprises boron-doped diamond. Such electrodes typically have a coating of boron-doped diamond. In the case of planar supports, the supports are preferably coated on both sides. Suitable support materials include, for example, niobium, titanium, molybdenum, tantalum, silicon, silicon carbide, glassy carbon, or steel. The anode can be surrounded on one or both sides by the anolyte, i.e., the liquid located in the anode compartment.

[0037] An aqueous solution of lithium sulfate is used as the anolyte. This typically has a pH value in the range of pH 0 to pH 9, particularly in the range of pH 0 to pH 7, and especially in the range of pH 0 to pH 5, measured at 25°C and 1 bar using a pH electrode. A pH value of pH 9 is usually obtained when dissolving lithium sulfate in deionized water. Lower pH values ​​of the anolyte are achieved, for example, by adding sulfuric acid.

[0038] The concentration of lithium sulfate in the anolyte is typically in the range of 0.5 mol / L up to the saturation concentration of lithium sulfate in water. Preferably, the concentration of lithium sulfate in the anolyte is in the range of 1 to 3 mol / L.

[0039] To promote the oxidation reaction, it is further advantageous if the pH of the anolyte does not fall below 0.5. Therefore, to stabilize the pH, it is beneficial if the lithium ion concentration in the anolyte at the start of electrolysis is in the range of 0.1 to 10 mol / L. Preferably, the lithium ion concentration in the anolyte during electrolysis is selected to be in the range of 1 to 8 mol / L, and particularly in the range of 2 to 6 mol / L.

[0040] It may be advantageous to add sulfuric acid to the anolyte before starting electrolysis, so that the pH value at the beginning of electrolysis is a maximum of pH 7. Preferably, the pH value of the anolyte should not be lowered below pH 1 before starting electrolysis.

[0041] Not least due to the electrolysis of water, which occurs as a side reaction and produces oxygen and protons, the pH of the anolyte drops below pH 5 during electrolysis, for example, to values ​​in the range of pH 0 to < pH 5. This drop in pH can also be partly attributed to the fact that the transport of lithium ions from the anode compartment to the cathode compartment is faster than the formation of lithium peroxodisulfate in the anode compartment. Furthermore, the transport of lithium ions from the anolyte through the separator to the catholyte also transports water of hydration from the anolyte to the catholyte, leading to a reduction in the volume of the anolyte and / or an increase in the concentration of hydrogen. + -ions in the anolyte, thus also leading to a decrease in pH value.

[0042] Preferably, during electrolysis, lithium sulfate is added to the anode compartment to equalize the lithium ion concentration. In particular, the process involves removing anolyte enriched with lithium peroxodisulfate from the anode compartment and adding lithium sulfate to the remaining anolyte. This can be done discontinuously or continuously. For example, fresh lithium sulfate can be added to the anolyte, preferably in the form of an aqueous solution of lithium sulfate, preferably having a pH value in the range of pH 0 to pH 7, specifically in the range of pH 0 to pH 5, measured at 25°C and 1 bar using a pH electrode. Preferably, the second solution obtained in step iii), which contains lithium in the form of a dissolved salt and sulfate, is added to the anolyte, optionally in combination with fresh lithium sulfate as described above.This increases the efficiency of lithium peroxodisulfate production, based on the amount of lithium peroxodisulfate used, and minimizes any losses of sulfate and lithium.

[0043] In a preferred embodiment of the invention, the contents of the anode compartment of the divided electrolysis cell are mixed. Any mechanical stirrer known to those skilled in the art can be used for this mixing of the cell contents. Mixing can also be achieved by pumping the anolyte. For example, an aqueous solution of lithium sulfate can be pumped from a reservoir through the anode compartment, thus circulating the anolyte.

[0044] In the cathode compartment, hydrogen is formed through the reduction of water. This process naturally produces hydroxide ions. During electrolysis, lithium ions migrate from the anode compartment through the separator into the cathode compartment, resulting in the overall reaction of lithium hydroxide, which accumulates in the catholyte, i.e., the aqueous liquid in the cathode compartment.

[0045] Typically, an aqueous solution containing lithium hydroxide is used as the catholyte. The lithium hydroxide concentration in the catholyte at the start of electrolysis is usually in the range of 0.01 to 4 mol / L, particularly in the range of 0.2 to 0.7 mol / L. Since the lithium hydroxide concentration in the catholyte increases during electrolysis, it can be easily used to obtain lithium salts in step iv). Preferably, a lithium ion concentration or a lithium hydroxide concentration in the catholyte in the range of 0.2 to 0.7 mol / L is maintained during electrolysis to ensure low cell resistance. Preferably, a portion of the catholyte is removed from the cathode compartment and replaced with water.Alternatively, or in combination with this, one can proceed by removing some or all of the lithium from the removed catholyte and returning the lithium-depleted catholyte to the cathode compartment. In this way, the removed catholyte is at least partially replaced by the lithium-depleted catholyte. This can be done discontinuously or continuously.

[0046] In a preferred embodiment of the invention, the contents of the cathode compartment of the divided electrolysis cell are mixed. Any mechanical stirrer known to those skilled in the art can be used for this mixing of the cell contents. Mixing can also be achieved by pumping the catholyte. For example, an aqueous solution of lithium hydroxide can be pumped from a reservoir through the cathode compartment, thus circulating the catholyte.

[0047] In principle, all materials exhibiting high alkali stability are suitable as cathode materials. Examples include stainless steel, titanium, graphite, boron-doped diamond, lead, brass, copper, nickel, platinum, and platinized electrodes. Preferably, the cathode material of the split electrolysis cell is stainless steel, for example, in the form of sheets, meshes, or grids that can be surrounded by the catholyte on one or both sides.

[0048] Furthermore, the electrolysis in step i) can be carried out by electrolysis of aqueous sodium sulfate in analogy to the production of sodium peroxodisulfate and sodium hydroxide described in WO 97 / 07262.

[0049] Applying the electrolysis voltage to the anodes and cathodes causes an electric current to flow through the electrolyte. The electrolysis voltage in step i) is typically in the range of 3 to 10 V, particularly 4 to 8 V. To avoid side reactions and damage to the electrode material, a current density of 1000 mA / cm² is generally used. 2 , especially 800 mA / cm 2 , not to be exceeded. The current densities at which the procedure is carried out are generally 50 to 1000 mA / cm². 2 preferably 100 to 800 mA / cm 2 .

[0050] The total duration of electrolysis in step i) naturally depends on the electrolysis cell, the amounts of substances in the system, the electrode areas used, and the current density. An optimal duration can be determined by a person skilled in the art through routine experiments, e.g., by taking samples during electrolysis. Generally, the electrolysis is carried out such that a peroxodisulfate concentration in the anolyte in the range of 0.1 to 2 mol / L is achieved.

[0051] Typically, the amount of current required to achieve a quantitative conversion is in the range of 1 to 12 A (96500 - 1158000 Coulomb / Mol) based on the amount of electrons transferred to lithium sulfate.

[0052] It has proven advantageous to oxidize only a portion of the sulfate contained in the anolyte to peroxodisulfate. This prevents an excessive drop in the sulfate concentration in the anolyte. In this way, high current efficiencies (Farady efficiency) of at least 85%, and in particular at least 90% or more, can be achieved. Specifically, the electrolysis will be carried out such that the conversion of sulfate to peroxodisulfate does not exceed 75%, and in particular not exceeding 50%, based on the total sulfate contained in the anode compartment. Specifically, the electrolysis will be carried out such that the conversion of sulfate to peroxodisulfate is in the range of 5 to 50%, and in particular in the range of 15 to 30%, based on the total sulfate contained in the anode compartment.

[0053] To achieve optimal Ra-time yields, various electrode geometries are known to those skilled in the art. The essential requirement is that the anode and cathode are separated by a separator, so that the anolyte and catholyte are spatially separated.

[0054] Suitable configurations include, for example, arrangements of electrode sheets, bipolar arrangements of multiple electrodes, arrangements in which a rod-shaped anode is enclosed by a cylindrical cathode, or arrangements in which both the cathode and the anode consist of a wire mesh that has been stacked on top of each other and coiled cylindrically. The distance between each electrode and the membrane is typically in the range of 0 to 30 mm. Both pot cells and flow cells are suitable as electrolysis cells, with the latter being preferable for continuous or batch operation due to their high current efficiency and energy efficiency. Furthermore, they allow for the recirculation of the catholyte and anolyte.

[0055] The electrolysis in step i) is usually carried out at a temperature in the range of 10 to 100 °C, preferably 20 to 80 °C, particularly 30 to 70 °C.

[0056] In step i), the electrolysis is generally carried out at a pressure below 2000 kPa, preferably below 1000 kPa, particularly below 150 kPa, e.g. in the range of 50 to 1000 kPa, particularly 80 to 150 kPa. It is particularly preferred to carry out the process according to the invention at a pressure in the range of atmospheric pressure (101 ± 20 kPa).

[0057] Step i) can be carried out successfully both discontinuously and continuously. The process according to the invention can also be carried out on an industrial scale. Suitable electrolysis cells are known to those skilled in the art. All embodiments of this invention relate to both laboratory and industrial scales.

[0058] Step ii)

[0059] In step ii), the sulfuric aqueous solution of lithium peroxodisulfate obtained in step i) is used to digest the black mass. In other words, step ii) follows step i). When the black mass is treated with the sulfuric aqueous solution of lithium peroxodisulfate obtained in step i), the lithium contained in the black mass, the aluminum usually present in the black mass, and at least some of the transition metals present in the black mass dissolve. This solution is subsequently referred to as the first aqueous solution.This contains the lithium and aluminum present in the black mass, as well as at least some of the transition metals present in the black mass in the form of their salts, particularly in the form of sulfates. The lithium, aluminum, and transition metals may also be present in the form of phosphates if the black mass contains phosphate, e.g., iron(III) phosphate, lithium iron(II) phosphate, or phosphate from the hydrolysis of hexafluorophosphate from conducting salts such as lithium hexafluorophosphate. The digestion is typically carried out by treating the black mass with the aqueous solution of lithium peroxodisulfate prepared in step i). For this purpose, the required amount of the aqueous solution of lithium peroxodisulfate is drawn from the anode compartment and mixed with the black mass in a reaction vessel.Preferably, the solids content of the mixture is adjusted to be in the range of 2 to 20 wt.%, in particular 5 to 15 wt.%, e.g. 8 to 12 wt.%. This ensures good mixing during treatment and a sufficiently low viscosity so that the mixture can be easily pumped.

[0060] Preferably, the pH of the aqueous sulfuric acid solution of lithium peroxodisulfate used for this purpose is selected such that it has a pH value, measured at 25°C and 1 bar with a pH electrode, below pH 2, in particular a maximum of pH 1.5, and specifically a maximum of 1. Should the aqueous solution of lithium peroxodisulfate produced in the anode compartment during electrolysis have a higher pH value, this pH value is preferably adjusted accordingly by adding sulfuric acid.

[0061] According to the invention, a black mass obtained from the mechanical reprocessing of a lithium battery is treated. This can be a primary or secondary lithium battery. For information on obtaining the black mass, reference is made to the literature cited above. In particular, the method for treating black mass from the mechanical reprocessing of secondary lithium batteries, i.e., lithium-ion accumulators, has proven successful. These can be secondary lithium batteries from electromobility, secondary lithium batteries used for storing solar and wind power, secondary lithium batteries from computer and / or telecommunications technology, secondary lithium batteries from power tools such as cordless screwdrivers, cordless saws, or household appliances such as cordless vacuum cleaners or garden equipment such as cordless lawnmowers (so-called...).Power tools) and other electrically powered devices, such as e-cigarettes.

[0062] These black masses typically contain, in addition to lithium, multivalent metals such as aluminum, possibly lead, and one or more transition metals such as copper, iron, nickel, cobalt, manganese, and / or vanadium, as well as carbon. The lithium content in the black mass is typically in the range of 0.2 to 10 wt.%, particularly in the range of 1 to 5 wt.%. The carbon contained in the black mass is typically present predominantly, particularly at least 90 wt.%, as graphite. The carbon content is typically in the range of 1 to 70 wt.%, frequently in the range of 10 to 70 wt.%, and particularly in the range of 30 to 65 wt.%, based on the black mass. The black mass often has a copper content in the range of 0.1 to 25 wt.%, and particularly in the range of 0.5 to 5 wt.%, based on the black mass.Furthermore, blackening compounds typically contain phosphorus in the form of phosphate and / or in the form of phosphorus-fluorine compounds that hydrolyze to phosphate. The blackening compound typically contains the aforementioned components in the following proportions, although these amounts can vary considerably depending on the origin and quality of the compound. All contents given here and below in wt.% are based on the dry weight of the blackening compound. The dry weight corresponds to the dry weight determined according to DIN 14346:2007-03 by drying the blackening compound at 105°C. The contents are typically as follows:

[0063] Lithium: 0.2 to 10.0 wt.%

[0064] Aluminum: 0.2 to 25.0 wt.%

[0065] Iron: 0 to 30.0 wt.%

[0066] Copper: 0.1 to 25.0 wt.%

[0067] Cobalt: 0 to 30.0 wt.%

[0068] Nickel: 0 to 30.0 wt.%

[0069] Manganese: 0 to 20.0 wt.%

[0070] Vanadium: 0 to 1.0 wt.% Fluorine: 0 to 10.0 wt.%

[0071] Phosphorus: 0 to 20.0 wt.% Carbon: 1 to 70 wt.%.

[0072] The treatment of the black mass in step ii) can be carried out at room temperature or at elevated temperatures, e.g., at a temperature of at least 30 °C, in particular at a temperature of at least 40 °C, e.g., at a temperature in the range of 30 to 100 °C, in particular in the range of 40 to 95 °C. In principle, higher temperatures, for example up to 130 °C or up to 110 °C, are also conceivable. In these cases, the digestion will be carried out under pressure. The duration of the treatment can be varied. As a rule, the treatment will be carried out until at least 90 mol% of the lithium contained in the black mass dissolves and until at least 20 mol%, in particular at least 50 mol%, specifically at least 70 mol% or at least 80 mol% of the polyvalent metals contained in the black mass, in particular aluminum and transition metals, dissolve. For this purpose, the black mass is usually left for at least 4 hours to several days, e.g.,4 h to 96 h, in particular 8 h to 72 h, in contact with the aqueous, sulfuric acid solution of lithium peroxodisulfate obtained in step i). The amount of aqueous, sulfuric acid solution of lithium peroxodisulfate obtained in step i) is chosen such that at least the amount of lithium peroxodisulfate theoretically required to dissolve the lithium and the polyvalent metals such as aluminum, possibly lead and transition metals, is used in step ii). The amount required for this purpose can be easily estimated by a person skilled in the art from the analytically determined content of lithium and polyvalent metals, such as aluminum, possibly lead and transition metals, in the black mass and the concentration of lithium peroxodisulfate in the aqueous sulfuric acid lithium peroxodisulfate solution obtained in step i) according to the following reaction equation (2): x LizSzOs + a Cu + b Al + c LiFePO4 + d LiNi. y Mn z Coi-y-zO2 -> 2x SO4 2 “ + a Cu 2++ b Al 3+ + (c+d+2x) Li + + c FePO4+ d Ni y Mn z Coi-y-zO2 (2)

[0073] Here, x represents the molar amount of lithium peroxodisulfate used, and the parameters a, b, c, and d represent the molar amounts of copper, aluminum, lithium iron(II) phosphate, and LiNi contained in the swarm mass. y Mn z Coi-y-zO2. The theoretical minimum amount of lithium peroxodisulfate then corresponds to the following equation (3) x = a + 2 / 3b + 0.5c + 0.5d (3)

[0074] To promote the digestion, it has proven advantageous to mix the black mass and the aqueous, sulfuric acid solution of lithium peroxodisulfate obtained in step i), e.g. by stirring, shaking or combinations of these measures.

[0075] Typically, the black mass contains, in addition to lithium, aluminum, and transition metals, materials that are insoluble in the aqueous, sulfuric lithium peroxodisulfate solution. These therefore remain as a solid after treatment. These include primarily carbon, possibly together with insoluble salts and / or organic materials. As a rule, before further processing of the first aqueous solution obtained in step ii), a separation of the undissolved material is carried out prior to step iii). This separation can be performed in a manner known per se by solid-liquid separation, such as filtration, decantation, centrifugation, or a combination of these methods. The resulting solid, in turn, represents a raw material for battery production, e.g., for lithium batteries, and can therefore be used accordingly.

[0076] Step iii)

[0077] In step iii), the polyvalent metals, especially the transition metals and aluminum, as well as any phosphate present, are partially or completely removed from the solution obtained in step ii). In this way, the transition metals are recovered as a valuable resource, and a second aqueous solution, depleted of polyvalent metals and any phosphate, is obtained, containing lithium in the form of a dissolved salt and sulfate. As already mentioned, the lithium can be recovered from this second solution. Furthermore, this second aqueous solution can be fed into the anolyte as a source of lithium sulfate and electrochemically oxidized to lithium peroxodisulfate in step i).

[0078] The removal of polyvalent metals, in particular the transition metals, aluminum, any iron, lead, and phosphate present, can be carried out by precipitation in a manner known per se. The transition metals can also be removed by electrolysis and, if necessary, separated from one another by refining. Of course, it is also possible to remove some or all of the transition metals, at least partially, by selective precipitation. For example, iron phosphate, iron hydroxide, aluminum phosphate, lead sulfate, lead phosphate, and / or aluminum hydroxide can be removed from the first solution by precipitation, while at least some of the other transition metals are removed partially or completely by electrolysis.Remaining transition metals that are not depleted by recovery electrolysis can also be precipitated, for example as hydroxides, sulfates, or phosphates, and thus depleted. In the case of manganese, selective separation can also be achieved by further oxidation, exploiting the formation of insoluble manganese dioxide (MnO₂). In particular, step iii) comprises the electrochemical deposition of at least some of the transition metals contained in the first aqueous solution, especially those transition metals whose standard potential in a dilute aqueous solution at pH 2 against the standard hydrogen electrode at 25 °C and 1 bar is at least -0.5 V. This depletion is typically carried out as recovery electrolysis, i.e., in the form of electrolysis in which the transition metal(s) are reduced by electrolysis at the cathode and deposited thereon as metal.

[0079] The electrochemical removal of at least some of the transition metals contained in the first aqueous solution can be carried out in a manner known per se, as described, for example, in Modern Electroplating, Schlesinger, Mordechay, Paunovic, Milan (eds.), Electrochemical Society Series, 5th edition 2010, New York, Wiley & Sons Ltd. It is typically performed at pH values ​​below pH 5, particularly at pH 2 or lower. For this purpose, the aqueous solution obtained in step ii) is electrolyzed. Electrolysis is generally carried out at temperatures in the range of 10 to 50 °C. The electrolysis is usually performed in undivided electrolysis cells.

[0080] Preferably, the electrochemical depletion of at least a part of the transition metals contained in the first aqueous solution takes place before precipitation of the remaining metal salts, since the former usually occurs at low pH values ​​of usually < pH 5, in particular at most pH 2, while the latter takes place at pH values ​​of at least pH 5, in particular at least pH 7.

[0081] In a preferred embodiment of step iii), copper is electrochemically depleted from the first solution. Preferably, the electrochemical deposition is carried out as recovery electrolysis, in which the copper is deposited as metallic copper on the cathode. The electrolysis of copper-containing solutions for copper extraction has long been known and can be carried out analogously for copper depletion and thus also for copper recovery. Preferably, the electrolysis is carried out at pH values ​​of at most pH 2, particularly at pH values ​​in the range of pH 0 to pH 2. The electrolysis can, for example, be carried out at temperatures in the range of 10 to 50 °C. The electrolysis is generally carried out in undivided electrolysis cells. Preferably, the electrolysis is potentiostatic. Preferably, voltages in the range of 2 to 4 V are used. The current density is preferably in the range of 1 to 20 mA / cm². 2Preferably, at least 90%, and in particular at least 95%, of the copper contained in the first aqueous solution will be removed in this way.

[0082] As an alternative to electrolysis, or following electrolysis, the transition metals can also be removed by precipitation from the initial aqueous solution. This method also removes any polyvalent metals, such as aluminum, transition metals, and possibly lead, and any phosphate present in the initial aqueous solution. For this purpose, the pH is raised by adding a base, generally to a pH of at least 5, and preferably at least 6, e.g., pH 5 to pH 12 or pH 6 to pH 11. This causes the polyvalent metals, i.e., the transition metals and aluminum, as well as any lead, to precipitate in the form of their hydroxides and, if applicable, in the form of their phosphates and / or sulfates. The separation can be carried out selectively by controlling the pH.

[0083] Ideally, lithium hydroxide and / or lithium carbonate are used as the base to prevent the introduction of foreign ions. Preferably, the pH can be raised to the desired value by adding catholyte removed from the electrolysis.

[0084] If necessary, the pH can be raised stepwise to achieve selective precipitation of the different metals. For example, raising the pH to the range of pH 5 to pH 8 is usually sufficient to quantitatively precipitate the aluminum, copper, and iron dissolved in the initial solution. A further increase in pH to pH 10 or higher then leads to the quantitative precipitation of manganese, cobalt, and nickel. Alternatively, the manganese salts can be oxidized to manganese dioxide (MnO₂), for example, with permanganate, which is itself reduced to manganese dioxide, or using H₂O₂ under alkaline conditions. Electrochemical oxidation of the dissolved manganese salts to manganese dioxide (MnO₂) is also possible.

[0085] Typically, precipitation is carried out at temperatures in the range of 0 to 50 °C.

[0086] The resulting precipitates can be separated from the aqueous phase by known solid-liquid separation methods, for example, by filtration and / or centrifugation. These methods yield a second aqueous solution. This solution preferably contains the respective transition metals in less than 1% of the initial value, and particularly in concentrations of less than 0.05 wt% each, calculated as metal. The total concentration of transition metals and aluminum in the solution thus obtained is typically below 0.1 wt%, based on the aqueous solution.

[0087] Step iv)

[0088] Both the second aqueous solution obtained in step iii) and the catholyte contain lithium and are therefore fundamentally suitable sources for lithium recovery. Since both solutions generally have pH values ​​above 7, recovery is easily achieved in the form of lithium carbonate or lithium hydroxide, e.g., lithium hydroxide hydrate, as these have a comparatively low solubility in water, at least at low temperatures.

[0089] For example, the lithium salts in the aqueous solution obtained in step iii) can be easily converted to the poorly water-soluble lithium carbonate by reaction with CO2. This is then separated as a solid from the second aqueous solution obtained in step iii) in a manner known per se. In this way, a neutral or weakly acidic aqueous solution is obtained, which essentially contains only lithium sulfate and can be fed into the anode compartment, thus being available again for the production of lithium peroxodisulfate.

[0090] Similarly, the catholyte, which essentially contains only lithium hydroxide and water, can be used as a source for lithium recovery. Since it contains not only the lithium hydroxide used but also the lithium hydroxide that accumulates in the catholyte during electrolysis, the lithium contained in the black mass is indirectly recovered in this way.

[0091] The lithium hydroxide contained in the catholyte can be easily converted to the poorly water-soluble lithium carbonate by reaction with CO2, as described above, and then separated from the catholyte. Alternatively, the catholyte can be concentrated and the lithium it contains crystallized as lithium hydroxide hydrate by cooling. This can then be converted to anhydrous lithium hydroxide by drying.

[0092] The reaction of lithium hydroxide with CO2 is easily achieved by spraying the respective aqueous solution into an atmosphere or by introducing gaseous CO2 into the respective aqueous solution.

[0093] The following examples and illustrations serve to demonstrate the invention.

[0094] Figure 1: Flow diagram of a preferred embodiment of the process according to the invention without selective separation of any aluminum or various transition metals that may be present.

[0095] In the process shown in Figure 1, the anode compartment (1a) of a split electrolysis cell (1) is filled with the anolyte (AL), i.e., an aqueous solution of lithium sulfate, and the cathode compartment (1l) with the catholyte (KL), i.e., an aqueous solution of lithium hydroxide. By applying an electric current, the lithium sulfate contained in the anolyte (AL) is oxidized at the anode (11) of the anode compartment (1a) until the desired conversion to lithium peroxodisulfate is achieved. In the cathode compartment (1l), hydrogen is formed at the cathode (12) and is extracted from the gas phase of the cathode compartment (1l). For reasons of electroneutrality, during electrolysis, the lithium ions released by the oxidation of the lithium sulfate and the protons formed as a side reaction of water oxidation at the anode migrate through the membrane (1l) from the anode compartment (1a) to the cathode compartment (1l).During electrolysis, the removed anolyte (AL) and catholyte (KL) can be replaced from corresponding storage vessels (not shown). The anolyte (AL) is removed from the anode compartment (1a) and transferred to a heated reactor (2) with a mixing element (2a) for the digestion of the black mass (BM). The black mass (BM) to be digested is added to the reactor (2) from a storage container (3) in the desired quantity, and the mixture is treated at the desired temperature while being thoroughly mixed. After digestion is complete, the reactor contents are subjected to a solid / liquid separation device (4), yielding a liquid extract (El) and a black mass (BM') depleted of lithium and metals. The liquid extract (El) is then, if necessary, after adjusting the pH to a value in the range of pH 0 to pH 2 (not shown), subjected to an electrolytic copper deposition (5), which is subjected as previously described.The resulting copper-depleted liquid extract (E2) is then transferred to a reactor (6) for the separation of further metals from the extract (E2). There, the remaining metals are precipitated as hydroxides and / or carbonates using lithium hydroxide or lithium carbonate. The precipitation can be carried out in stages to achieve a preliminary separation of the metals (not shown here). The contents of the reactor (6) are then subjected to a solid / liquid separation (7), yielding an aqueous solution (E3) containing dissolved lithium and sulfate, and a solid (Fl) containing the transition metals and, if present, lead and / or aluminum in the form of hydroxides. The solution (E3) is essentially free of metal salts other than lithium salts. Due to its sulfate content, the solution (E3) is typically returned to the anode compartment (1a) of the electrolysis cell (1).To obtain the high-purity lithium salts, the lithium hydroxide-enriched catholyte (KL') obtained during electrolysis is removed from the cathode compartment (lk). To precipitate the lithium hydroxide, the catholyte (KL') is treated with CO2 in a reactor (8), causing the lithium to precipitate as poorly soluble lithium carbonate. A solid / liquid separation (9) yields the depleted catholyte (KL), which can be reintroduced into the electrolysis process, and a high-purity lithium carbonate.

[0096] Examples

[0097] Step 1: Electrolytic production of an aqueous lithium peroxodisulfate solution: The electrolytic production was carried out in a split, flow-through electrolysis cell, which contained a niobium electrode (BDD electrode) coated on both sides with 12 pm boron-doped diamond as the anode. The BDD electrode had an active electrode area of ​​750 cm². 2The electrode was centrally positioned and surrounded on both sides by the anolyte. Two stainless steel electrodes, each surrounded on one side by the anolyte, served as the cathode. A Nafion electrode was used as a separator to divide the two electrode compartments. TM A membrane was used. The catholyte consisted of 5 L of an aqueous 0.25 molar LiOH solution. The anolyte was 4 L of an aqueous sulfuric acid solution at concentrations between 1.8 and 3 mol / L. The two solutions were pumped from two separate electrolyte reservoirs through the electrolysis cell at a flow rate of 10 to 15 L / min (semi-batch operation). The electrolysis current was kept constant at either 75, 100, or 150 A, resulting in a current density of 100, 133, or 200 mA / cm², respectively. 2This corresponded to the above. In each of the experiments, a charge of 2 F was applied. By electrolysis, strongly acidic solutions (pH < 1) of lithium peroxodisulfate with concentrations in the range of 0.1 to 0.53 mol / L were obtained on the anode side. The average voltage during electrolysis was between 6.7 and 8.3 V. During electrolysis, approximately 20% of the anolyte volume was transferred across the membrane to the cathode side. As described below in step 3b, this volume transfer could be compensated for.

[0098] Step 2: Dissolution of the black mass with lithium oeroxodisulfate solution:

[0099] The aqueous lithium peroxodisulfate solution obtained in step 1 was mixed with 40 to 150 g of the black mass per liter of solution, depending on the solution concentration and the starting material of the black mass used, and stirred for up to 2 days at 50 °C. The remaining solid was then filtered off. In addition to lithium, the resulting filtrate contained dissolved manganese, iron, cobalt, nickel, copper, and aluminum in the concentrations listed in Table 1. The efficiency of the lithium extraction was >96%.

[0100] In this step, black masses of different compositions were used. The black masses used contained

[0101] Lithium: 1.8 to 4.1 wt.%

[0102] Aluminum: 1.1 to 8.3 wt.%

[0103] Iron: 0.6 to 22.1 wt.%

[0104] Copper: 2.0 to 7.4 wt.%

[0105] Cobalt: 0.2 to 12.3 wt.%

[0106] Nickel: 0.8 to 24.1 wt.%

[0107] Manganese: 0.3 to 3.1 wt.%

[0108] Phosphorus: 1.3 to 8.0 wt.%

[0109] Carbon: 25.1 to 67.8 wt.%

[0110] Analysis was performed using XRF and ICP-OES (lithium). The values ​​given refer to the dry mass of the black mass. Table 1: Concentration ranges of dissolved metals after digestion of the black mass. 1 )

[0111] 1) The variation in metal content is due to the different composition of the black masses used.

[0112] Step 3: Removing metals and, if necessary, phosphate:

[0113] Step 3a: Electrochemical deposition of copper

[0114] The solution obtained as filtrate after digestion in step 2 served as the electrolyte for copper deposition. A single-cell electrolysis unit, consisting of a copper cathode and a lead anode, was used for the electrolysis. The active electrode area was 156 cm² in each case. 2 The electrodes were 2 cm apart. Copper deposition was carried out under potentiostatic conditions at a cell voltage of 2.4 V until the current flow dropped to a constant value. During the electrochemical copper deposition, the copper grew in compact form on the cathode. Approximately 98% of the dissolved copper could be extracted from the solution.

[0115] Step 3b: Precipitation of transition metals, aluminum, and possibly phosphate.

[0116] Precipitation was initiated by raising the pH of the copper-depleted solution obtained in step 3a from pH <1 to pH >7 according to one of the two precipitation methods described below. The metals precipitated mostly as the corresponding hydroxide salts, with a small portion also precipitating as the corresponding sulfate salts. When using lithium iron phosphate-containing black mass, the dissolved iron also precipitated as a phosphate salt.

[0117] Since, as described below, the strongly basic catholyte solution was used in both precipitation procedures, the volume loss of anolyte observed in step 1 was compensated for by the corresponding catholyte removal. Furthermore, solid LiOH'H₂O and solid Ü₂CO₃, respectively, were used in the two precipitation procedures. These two lithium salts were recovered from the catholyte as described in step 4. Steps 3b-1: Precipitation with LiOH:

[0118] The solution obtained in step 3a was mixed with the strongly basic catholyte solution, and the pH of the mixture was raised to >7 by adding solid LiOH'H₂O. Between 0.2 and 0.3 L of catholyte solution were added relative to the initial starting volume (based on step 1). Between 72 and 75 g of LiOH'H₂O were required to adjust the pH to 7.5. A total of 137 g of LiOH'H₂O was required to raise the pH to 10.

[0119] Step 3b-2: Failure with LbCCk:

[0120] The pH of the solution obtained in step 3a was first raised to pH > 2 by adding solid Li₂CO₃. The strongly basic catholyte solution was then added, resulting in a pH of at least pH 9. Initially, the elements Cu, Fe, Al, and Mn precipitate in the form of their hydroxides or phosphates. By further increasing the pH to pH > 10, additional elements, namely nickel and cobalt, can be precipitated in the form of their hydroxides and / or possibly phosphates (if phosphate is still present in the solution).

[0121] As can be seen from Table 2, the metals manganese, iron, cobalt, nickel, copper and aluminium, which were present in dissolved form in the solution obtained in step 3a, could each be precipitated almost quantitatively using the two precipitation methods described above.

[0122] Table 2. Efficiencies of metal precipitation in step 3b

[0123] *) When the pH value is increased to >10.

[0124] The solution obtained in step 3b, which had been depleted of transition metals, aluminium and, if applicable, phosphate, was partially or completely recycled back into the electrolysis in step 1 and thus served as the starting solution for the renewed electrochemical production of lithium peroxodisulfate.

[0125] Step 4: Extraction of lithium as LiOH or LhCCh:

[0126] The following two processes were used to separate the lithium that accumulated in the catholyte during the electrochemical production of lithium peroxodisulfate. Either lithium carbonate or lithium hydroxide was obtained. Step 4a: Precipitation of IJ₂CO₃:

[0127] U₂CO₃ was precipitated by introducing carbon dioxide into the strongly basic catholyte solution. For this purpose, CO₂ was blown into the solution until the pH dropped to 10.5. The U₂CO₃ was then filtered off. After the dissolved carbon dioxide was driven off with an inert gas, such as nitrogen, the filtrate could be reused in step 1 as the catholyte for the electrochemical production of lithium peroxodisulfate. After drying at 110°C, the filtered Li₂CO₃ exhibited a purity of 99.6 mol% (based on the total amount of sodium and lithium). The small amounts of sodium originated from the deionized water used in the preparation of the catholyte and anolyte.

[0128] Step 4b: Crystallization of LiOH'H2O:

[0129] Cooling the catholyte solution to 8 °C allowed LiOH-H2O to crystallize. The crystals were then isolated by filtration. The filtrate was then separated again in step

[0130] 1. This substance was used as a catholyte for the electrochemical synthesis of lithium peroxodisulfate. The filtered crystals were converted to solid LiOH-H2O by drying at 110 °C. Further drying at 180 °C under vacuum yielded anhydrous LiOH.

Claims

1. A process for obtaining lithium salts from black mass from the mechanical recycling of lithium batteries, in particular lithium-ion accumulators, comprising the following steps: i) providing an aqueous sulfuric acid solution of lithium peroxodisulfate by electrolysis of an aqueous solution of lithium sulfate in a divided electrolysis cell, wherein an aqueous sulfuric acid solution of lithium peroxodisulfate and oxygen is obtained in the anode compartment of the divided electrolysis cell, and an aqueous lithium hydroxide solution and hydrogen are obtained in the cathode compartment of the divided electrolysis cell;ii) Treatment of the black mass with the aqueous sulfuric solution of lithium peroxodisulfate provided in step i), yielding a first aqueous solution containing the lithium present in the black mass in the form of its sulfates and / or phosphates, as well as at least some of the polyvalent metals present in the black mass in the form of their sulfates and / or phosphates; iii) Removal of the polyvalent metals and any phosphate present from the first aqueous solution, yielding a second aqueous solution depleted of polyvalent metals and any phosphate, containing lithium in the form of a dissolved salt and sulfate; iv) Recovery of the lithium in the form of a salt from the second aqueous solution and / or from the aqueous lithium hydroxide solution obtained in the cathode compartment.

2. The method of claim 1, wherein the anolyte is separated from the catholyte by a cation exchange membrane.

3. Method according to any of the preceding claims, wherein the anode material of the anode of the split electrolysis cell comprises boron-doped diamond.

4. Method according to one of the preceding claims, wherein the aqueous solution of lithium sulfate used in step i) has a pH value in the range of pH 0 to 9, in particular 1 to 7, measured at 25°C and 1 bar with a pH electrode. TI 5. A method according to any of the preceding claims, wherein the electrolysis in step i) is carried out such that the conversion of sulfate to peroxodisulfate is in the range of 5 to 50%, in particular in the range of 10 to 30%, based on the sulfate contained in the anode compartment.

6. Method according to one of the preceding claims, wherein anolyte is removed from the anode compartment and lithium sulfate is added to the anolyte remaining in the anode compartment.

7. The method of claim 6, wherein at least a part of the second aqueous solution obtained in step iii) is returned to the electrolysis.

8. Method according to one of the preceding claims, wherein the aqueous sulfuric solution of lithium peroxodisulfate used in step ii) for the treatment of the black mass has a pH value, measured at 25 °C and 1 bar with a pH electrode, below pH 5.

9. Method according to any of the preceding claims, wherein the first aqueous solution obtained in step ii) has a pH value in the range of pH 0 to pH 5, measured at 25°C and 1 bar with a pH electrode.

10. Method according to one of the preceding claims, wherein in step ii) following the treatment of the black mass, a separation of the first aqueous solution obtained from the undissolved material is carried out.

11. Method according to any of the preceding claims, wherein step iii) comprises an electrochemical deposition of at least a part of the transition metals contained in the first aqueous solution.

12. A method according to any of the preceding claims, wherein in step iii) the pH of the first aqueous solution is adjusted to a pH of at least pH 5, measured at 25°C and 1 bar with a pH electrode, by adding lithium hydroxide and / or lithium carbonate, thereby precipitating at least some of the polyvalent metals contained in the first aqueous solution.

13. The method of claim 12, wherein in step iii) an electrochemical deposition of at least a part of the transition metals contained in the first aqueous solution is carried out and subsequently the pH of the first aqueous solution is adjusted to a pH of at least pH 5, measured at 25°C and 1 bar with a pH electrode, by adding lithium hydroxide and / or lithium carbonate.

14. The method of claim 13, wherein, in particular, an aqueous solution of the lithium hydroxide obtained from the catholyte is used to adjust the pH value.

15. Method according to any of the preceding claims, wherein the second aqueous solution obtained in step iii) is partially or completely recycled back into the electrolysis in step i).

16. Method according to any of the preceding claims, wherein in step iv) the lithium is extracted from the catholyte as lithium carbonate or lithium hydroxide hydrate.

17. Method according to one of the preceding claims, wherein during electrolysis a portion of the catholyte is removed from the cathode compartment and replaced by water or by the lithium-depleted catholyte.

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