Device for recovering one or more metals comprising lithium from leaching solution derived from lithium-containing waste batteries

Abstract

The utility model relates to a device for recovering one or more metals containing lithium from a leaching solution from a lithium-containing waste battery, which comprises a pH (potential of hydrogen) adjusting unit 1 provided with an inlet for the leaching solution and an inlet for a pH adjusting reagent (such as acid or alkali); a reaction unit 2 having an inlet for an Al, F and / or Li-containing reagent to adjust the stoichiometric ratio of the reaction mixture such that it facilitates lithium cryolite formation; and a recovery unit 3 for recovering lithium cryolite, for example by precipitation, the recovery unit 3 comprising a lithium cryolite outlet and a separate outlet for the lithium-depleted solution.

Description

Technical Field

[0001] The utility model relates to a method for recovering one or more metals from battery materials, in particular to a method for extracting lithium from a leaching solution derived from waste batteries, and then performing optional further extraction. The utility model also relates to a device for recovering one or more metals including lithium from a leaching solution derived from waste batteries containing lithium. Background Art

[0002] The use of lithium-ion batteries has grown steadily over the past few years, and their importance looks set to grow further in the coming years. Lithium-ion batteries contain a variety of transition metals in their cathodes, and it is valuable to recover these metals from these batteries for reuse in new batteries or for other purposes. In particular, the lithium in these materials is valuable for recycling and reuse.

[0003] The hydrometallurgical separation of metals in lithium-ion batteries is carried out by recovering the black mass, which contains cathode metals and anode materials and from which the wires and other bulky solid battery components (such as plastic or steel parts) have been removed.

[0004] The next step is usually to separate the cathode metal from the other components of the black mass, for example using a mechanical, thermal or chemical pretreatment step, followed by acid leaching to dissolve the cathode metal in preparation for its recovery.

[0005] After leaching, the desired metals can be recovered. WO 2022 / 219223 A1 describes a method for recovering lithium and other metals from a leaching solution of battery black. However, in this method, the lithium recovery step is after other separation and recovery steps.

[0006] Since each step of this method carries the risk of metal loss, each step before lithium recovery will result in further lithium loss. However, the inventors have now found a new method for recovering metals from battery black matter that can reduce lithium loss. Utility Model Content

[0007] According to a first aspect of the utility model, a method for recovering one or more metals from waste batteries is provided.

[0008] According to a second aspect of the present invention, a method for recovering one or more metals including lithium (Li) from black matter obtained from waste batteries containing lithium is provided.

[0009] According to another aspect, a method for improving the recovery rate of metallic lithium from a black matter leaching solution is provided.

[0010] Therefore, the utility model relates to a method for recovering one or more metals including lithium from a leaching solution derived from lithium-containing waste batteries, the method comprising the following steps:

[0011] - Adjust the pH value of the lithium-bearing leaching solution to an acidic solution level of <7,

[0012] - adding one or more of aluminum (Al), fluorine (F) and lithium (Li) reagents to the acidic solution as needed to make all of these reagents available and adjust the stoichiometric balance of the reaction mixture and precipitate lithium cryolite, and

[0013] - Recovering the precipitated lithium cryolite from the reaction mixture solution.

[0014] The utility model focuses on precipitating lithium under low pH conditions (e.g., below 2) to obtain lithium cryolite (Li3AlF6). Lithium recovery occurs after the black matter of the battery material is leached, for example, using an acidic leaching solution containing sulfuric acid to obtain a leaching solution containing cathode metals, but before recovering any other metals.

[0015] The lithium concentration in the leach solution used as the starting material typically varies in the range of 4-8 g / l. Some aluminium (Al) and fluorine (F) may also be present in the solution, but cryolite can be precipitated from the solution by adjusting the stoichiometric balance of the acidified leach solution, adding further Al, F and / or Li reagents as required to match the stoichiometric ratio of lithium cryolite. The key step in precipitation is to have stoichiometric or higher dosages of Al and F. When this minimum stoichiometric ratio is reached, and the pH is low enough, lithium can be selectively precipitated as Li3AlF6. Precipitation rates are typically in the 80-90% range.

[0016] Precipitation can also occur at higher pH levels, such as in CN 113684369 A, but this will result in a loss of selectivity and purity since impurities will also be precipitated.

[0017] Several advantages are achieved by means of the utility model. In particular, the lithium loss that occurs in conventional methods is avoided, thereby achieving high selectivity in lithium recovery and being able to obtain a high-purity lithium product at a high yield.

[0018] Furthermore, when the lithium product obtained using the method of the present invention is purified, a battery-grade product will be obtained, which can be recycled for use in the preparation of cathodes for lithium-containing batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 A process arrangement for recovering lithium cryolite from a leaching solution of lithium-containing spent batteries according to at least some embodiments of the present invention is shown. DETAILED DESCRIPTION

[0020] definition

[0021] In this context, a "lithium-containing battery" is typically an NMC or LFP battery, and the present invention is particularly suitable for recovering metals from NMC batteries, but is also suitable for recovering metals from LFP batteries.

[0022] Therefore, the present invention is dedicated to recycling and recovering metals, such as lithium (Li), from leaching solutions of black matter originating from lithium-containing batteries. These batteries can be of NMC (or LFP) type. In addition to lithium, other battery metals, such as nickel (Ni), cobalt (Co) and manganese (Mn), as well as other components of black matter, such as copper (Cu), aluminum (Al), iron (Fe) and fluorine (F), are also recovered.

[0023] "NMC" batteries have a cathode formed using a mixed metal oxide of lithium, nickel, manganese and cobalt.

[0024] "LFP" batteries use lithium iron phosphate as the cathode.

[0025] Therefore, the utility model relates to a method for recovering one or more metals including lithium from a leaching solution of lithium-containing waste batteries, comprising the following steps:

[0026] - Adjust the pH value of the lithium-bearing leaching solution to an acidic solution level of <7,

[0027] - adding one or more of aluminum (Al), fluorine (F) and lithium (Li) reagents to the acidic solution as needed to make all of these reagents available and adjust the stoichiometric balance of the reaction mixture and precipitate lithium cryolite, and

[0028] - Recovering the precipitated lithium cryolite from the reaction mixture solution.

[0029] The utility model can be used, for example, Figure 1 The process arrangement shown is implemented, which includes a pH adjustment unit 1, which has an inlet for a leaching solution and an inlet for a pH adjustment reagent (such as an acid or a base); a reaction unit 2, which has an inlet for an Al-, F- and / or Li-containing reagent to adjust the stoichiometric ratio of the reaction mixture to favor the formation of lithium cryolite; and a recovery unit 3 for recovering the lithium cryolite, for example by precipitation, the recovery unit 3 comprising an outlet for lithium cryolite and a separate outlet for a lithium-poor solution.

[0030] Typically, the leaching solution used as starting material in the process is derived from the black mass of such lithium-containing batteries, which contains cathode metal and anode material, and from which wires and other gross solid battery components, such as plastic or steel parts, have been removed.

[0031] In one embodiment of the present invention, the leaching solution is derived from black mass obtained from NMC batteries, and in addition to lithium metal, it also contains one or more other metals, such as nickel (Ni), cobalt (Co) or manganese (Mn) or copper (Cu) and generally contains one or more impurities, such as iron (Fe), aluminum (Al) or fluorine (F).

[0032] The leach solution is preferably obtained by leaching under acidic conditions using a leach solution containing sulfuric acid, wherein the pH of the leach solution is already at or close to the desired acidic level before the pH adjustment of the utility model. Optionally, additional redox chemicals have been used for leaching, such as hydrogen peroxide, carbohydrates and sulfur dioxide, which provide more effective dissolution due to their redox ability.

[0033] Prior to lithium precipitation, the pH of the leaching solution used as starting material is adjusted to an acidic level, preferably to a level of ≤ 4, such as 0.5-3, such as 1-2, or such as 1.5-2.5.

[0034] Preferably, the pH is adjusted using an alkaline solution containing, for example, ammonium hydroxide, NaOH, KOH, Na2CO3, CaCO3, Ca(OH)2, or an acidic solution containing a mineral acid such as sulfuric acid (H2SO4) or hydrochloric acid (HCl), or a solution containing a suitable combination of such agents to provide the required alkalinity or acidity for pH adjustment. Since the leaching solution used as starting material usually already contains sulfuric acid, sulfuric acid is a preferred alternative for use in pH adjustment.

[0035] To promote efficient lithium precipitation, the content of lithium (Li), aluminum (Li) and fluorine (F) in the leaching solution is determined before or after pH adjustment, and if necessary, one or more of these components is obtained by adding Al, F and Li reagents to the solution. Preferably, sufficient amounts of these reagents are added to the acidified leaching solution to provide a Li:Al:F stoichiometric ratio of 3:0.8-2:4-8, or a Li:Al:F stoichiometric ratio of about 3:0.9-1:4-7.5, or a Li:Al:F stoichiometric ratio of about 3:0.9:4.2-7.2.

[0036] The reagent used to adjust the stoichiometric ratio in the acidified leaching solution is preferably selected from fluorine-containing compounds, such as ammonium fluoride or hydrofluoric acid, or aluminum-containing salts, such as aluminum sulfate, or lithium-containing compounds, such as lithium sulfate, lithium chloride, lithium fluoride.

[0037] After adjusting the contents of Li, Al and F in the acidified leaching solution to achieve the predetermined stoichiometric ratio, lithium is precipitated in the form of cryolite. The precipitation is allowed to proceed at a temperature of 5 to 100°C, such as 10 to 95°C or 20 to 80°C, such as 25 to 70°C or such as 40 to 60°C.

[0038] Likewise, the precipitation is preferably carried out at atmospheric pressure or at least close to atmospheric pressure, for example at a pressure of 0.5 to 5 bar, such as at a pressure of 1 to 5 bar.

[0039] The precipitate is preferably recovered from the remaining solution, ie from the solution of the reaction mixture, by solid-liquid separation, for example by filtration, thickening or a combination thereof.

[0040] In one embodiment of the present invention, the lithium cryolite obtained as a precipitate is further reacted into lithium hydroxide by an alkali process and recovered as monohydrate crystals.

[0041] In one embodiment of the present invention, the solution remaining after lithium cryolite recovery is conveyed to one or more separation steps to separate one or more of the impurities Al, Fe and F from the solution. These impurity separations are preferably carried out by precipitation, for example by hydroxide precipitation to provide precipitates of iron and aluminum, or by solvent extraction, or by precipitation and filtering any solid impurities followed by solvent extraction.

[0042] In another embodiment of the present invention, the solution remaining after the recovery of lithium cryolite is transported to one or more further recovery steps to recover one or more of the metals Ni, Co, Mn and Cu, which steps are preferably performed after the above-mentioned optional impurity separation.

[0043] In the case of copper recovery, it is preferably carried out before recovering Ni, Co and Mn, because copper can have a negative impact on these subsequent recovery and product quality. Copper recovery can be carried out, for example, in the following forms: solvent extraction (SX), precipitation (e.g., hydroxide precipitation), solvent extraction after precipitation, and substitution (cementation) using nickel as a reagent, which causes the Cu in the solution to be replaced by Ni, thereby obtaining a Cu metal product, which can be easily separated from the components of the solution. The substitution reaction is based on the nickel reagent having a higher or more negative reduction potential (-0.25V) than the reduction potential of copper (0.34V). The selectivity of the nickel reagent is based in part on the fact that the reduction potentials of other elements such as cobalt (-0.28V), manganese (-1.19V) or aluminum (-1.66V) present in the leaching solution are more negative than the reduction potential of the nickel reagent, so these elements will not be reduced.

[0044] In the case of nickel recovery in the leaching solution, nickel recovery is preferably carried out after copper separation, more preferably at the same time as or directly after the optional recovery of cobalt, and most preferably after the recovery of cobalt. Similarly, nickel recovery is preferably carried out after the optional recovery of manganese.

[0045] The optional nickel recovery can be carried out, for example, using solvent extraction (SX), which produces a fairly pure nickel sulfate solution (NiSO4). The solution is optionally further purified, for example by ion exchange (IX), and can then be crystallized or precipitated into hydroxides or carbonates, or the sulfate solution can be used directly without crystallization or precipitation, for example in the preparation of new cathode materials. The optional solvent extraction for nickel recovery is most preferably carried out using an extraction chemical having a carboxylic acid functional group, and a commercial example of a suitable extraction chemical is Versatic TM 10, which is neodecanoic acid.

[0046] Where cobalt recovery is performed, it is preferably performed simultaneously with nickel recovery or directly before nickel recovery, more preferably before nickel recovery. Similarly, cobalt recovery is preferably performed after optional manganese removal or recovery.

[0047] The preferred method for the optional cobalt recovery is solvent extraction (SX), which produces a fairly pure cobalt sulfate solution (CoSO4). The solution can be further purified, for example by ion exchange (IX), and can then be crystallized or precipitated into hydroxides or carbonates, or the sulfate solution can be used as is without crystallization or precipitation, for example in the preparation of novel cathode materials. The optional solvent extraction for cobalt recovery is most preferably carried out using an extraction chemical having a carboxylic acid functional group (e.g., a phosphinic acid functional group), and an example of a suitable extraction chemical is Cyanex TM 272, which is also known as trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate.

[0048] In an alternative way of performing metal recovery, as described above, cobalt and nickel can be recovered simultaneously from the leach solution, for example by solvent extraction, thereby producing a sulfate solution, optionally followed by further purification by ion exchange (IX), or precipitation into hydroxides or carbonates. Alternatively, the sulfate solution can be used directly without crystallization or precipitation, for example for the preparation of new cathode material.

[0049] Where separate recovery of manganese is carried out, it is preferably carried out prior to any recovery of nickel or cobalt.

[0050] The schemes for manganese recovery include solvent extraction, precipitation and crystallization, or solvent extraction followed by precipitation or crystallization. A particularly preferred scheme is oxidative precipitation using sulfur dioxide SO2 and air to form manganese oxide MnO2.

[0051] In summary, the utility model can be used to recover all valuable metals of the cathode of waste lithium batteries with high yield and high selectivity. In particular, compared with the prior art solutions, the selectivity of lithium recovery is improved.

[0052] In another aspect, the utility model relates to a device for recovering one or more metals including lithium from a leaching solution derived from a waste battery containing lithium, the device comprising:

[0053] a pH adjustment unit 1 having an inlet for the initial leaching solution, an inlet for the pH adjustment reagent and an outlet for the pH adjusted leaching solution;

[0054] - a reaction unit 2 for forming lithium cryolite, which has an inlet for an Al-containing reagent, a F-containing reagent and / or a Li-containing reagent, an inlet for a pH-adjusted leaching solution; and an outlet for a reaction mixture; the inlet for the pH-adjusted leaching solution of the reaction unit 2 is connected to the outlet for the pH-adjusted leaching solution of the pH adjustment unit 1;

[0055] as well as

[0056] - A recovery unit 3 for recovering lithium cryolite, the recovery unit 3 comprising an inlet for a reaction mixture from the reaction unit 2, an outlet for a lithium cryolite product and an outlet for a lithium-poor solution; the inlet for the reaction mixture from the reaction unit 2 of the recovery unit 3 is connected to the outlet for the reaction mixture of the reaction unit 2.

[0057] The layout of the device is as follows Figure 1 shown.

[0058] In one embodiment, the pH adjustment unit 1 further comprises a pH control unit to control the pH of the pH-adjusted leaching solution to ≤4, such as 0.5-3, such as 1-2, or such as 1.5-2.5.

[0059] In one embodiment, the reaction unit 2 further comprises a material control unit, so that the Li:Al:F stoichiometric ratio of the reaction mixture in the reaction unit 2 is 3:0.8-2:4-8, or about 3:0.9-1:4-7.5, or about 3:0.9:4.2-7.2.

[0060] In one embodiment, the recovery unit 3 further comprises a temperature control unit so that the temperature in the recovery unit 3 is 5 to 100°C, such as 10 to 95°C or 20 to 80°C, such as 25 to 70°C or such as 40 to 60°C.

[0061] In one embodiment, the device further comprises a solid-liquid separation unit, preferably a filtration unit, to separate the lithium cryolite as a precipitate from the remaining solution.

[0062] In one embodiment, the apparatus further comprises one or more other separation units, which are arranged after the recovery unit 3 to separate one or more of the impurities Al, Fe and F from the remaining solution.

[0063] In one embodiment, the apparatus further comprises one or more metal recovery units arranged after one or more other separation units to recover one or more of the metals Ni, Co, Mn and Cu from the remaining solution.

[0064] In one embodiment, the apparatus further comprises one or more copper recovery units, which are arranged after the recovery unit 3 to recover copper from the remaining solution.

[0065] In one embodiment, the apparatus further comprises one or more nickel and / or cobalt recovery units, which are arranged after the recovery unit 3 to recover nickel and / or cobalt from the remaining solution.

[0066] In one embodiment, the apparatus further comprises one or more manganese recovery units, which are arranged after the recovery unit 3 to recover manganese from the remaining solution.

[0067] It should be understood that the disclosed embodiments of the present invention are not limited to the specific structures, process steps or materials disclosed herein, but are extended to equivalents thereof that will be recognized by those skilled in the relevant art. It should also be understood that the terms used herein are used for the purpose of describing specific embodiments, and are not intended to be limiting.

[0068] The "one embodiment" or "an embodiment" mentioned in this specification means that the specific features, structures or characteristics described in association with the embodiment are included in at least one embodiment of the utility model. Therefore, the phrases "in one embodiment" or "in an embodiment" appearing in various places throughout this specification do not necessarily refer to the same embodiment.

[0069] As used herein, for convenience, multiple items, structural elements, constituent elements and / or materials can be listed in a general list. However, these lists should be understood as each member in the list being individually identified as a separate and unique member. Therefore, in the absence of contrary instructions, any single member in the list should not be interpreted as being in fact equivalent to any other member in the same list simply based on its presentation in a common group. In addition, various embodiments and examples of the utility model can be mentioned herein together with alternatives to its various parts. It should be understood that such embodiments, embodiments and alternatives should not be interpreted as being in fact equivalent to each other, but should be regarded as independent and separate presentations of the utility model.

[0070] In addition, the described features, structures or characteristics can be combined in any suitable manner in one or more embodiments. In the following description, many specific details are provided, such as examples of length, width, shape, etc., to provide a thorough understanding of the embodiments of the present invention. However, those skilled in the relevant art will recognize that the present invention can be implemented without one or more specific details, or implemented using other methods, components, materials, etc. In other cases, well-known structures, materials or operations are not shown or described in detail to avoid confusing various aspects of the present invention.

[0071] Although the above examples illustrate the principles of the present invention in one or more specific applications, it is obvious to those skilled in the art that many modifications can be made in form, usage and implementation details without exercising the inventive ability and without departing from the principles and inventive concepts of the present invention. Therefore, it is not expected that the present invention will be limited unless limited by the following claims.

[0072] The verbs "comprise" and "include" as used herein are open-ended limitations that neither exclude nor require the presence of unrecited features. The features recited in the appended claims are mutually freely combinable unless expressly stated otherwise. Furthermore, it should be understood that the terms "a" or "an" used throughout this disclosure, i.e. in the singular, do not exclude the plural.

[0073] Industrial Applicability

[0074] The present method can be used to replace the conventional scheme for recovering metals from black matter obtained from lithium-ion batteries.

[0075] In particular, the process provides an economical and efficient method for recovering lithium and optionally other metals from such battery materials in good yields. By performing lithium recovery prior to any further metal recovery, the lithium yield is particularly increased.

[0076] Reference List

[0077] Patent Literature:

[0078] CN 113684369 A

[0079] WO 2022 / 219223 A1

[0080] Example

[0081] The black matter is dissolved with a suitable mineral acid and a leaching agent to obtain a leaching solution containing valuable metals such as Li, Ni, Co, Cu, Mn, etc. The leaching solution thus obtained is used for lithium precipitation tests. One liter of the leaching solution is placed in a reactor. The temperature is adjusted to the target value, and the stoichiometric ratio of Li:Al:F is adjusted by adding a suitable reagent containing Li, Al and / or F. Then, the pH is adjusted accordingly, after which it is left for 1 hour and then the corresponding sample is taken to determine the residual concentration of the metal ions in the solution. The following example shows the effect of temperature, pH and the stoichiometric ratio of Li:Al:F on the lithium and aluminum yields.

[0082] Example 1

[0083] In Example 1, the temperature and pH were kept constant (T=80° C. and pH=1.5), and only the stoichiometric ratio of Li:Al:F was changed.

[0084] Table 1. Effect of Li:Al:F stoichiometric ratio on Li and Al yields

[0085]

[0086] It can be seen from Table 1 that it is advantageous to use a slightly excess of F when precipitating Li. The highest Li yield was obtained when the amount of fluoride reagent exceeded 1.2 times.

[0087] Example 2

[0088] In Example 2, the stoichiometric ratio of Li:Al:F and pH were kept constant (Li:Al:F=3:0.9:7.2 and pH=1.5), and only the temperature was varied.

[0089] Table 2. Effect of temperature on Li and Al yields

[0090]

[0091] As can be seen from Table 2, the highest Li yield was obtained at 65 °C.

[0092] Example 3

[0093] In Example 3, the temperature and the stoichiometric ratio of Li:Al:F were kept constant (T = 80°C and Li:Al:F = 3:0.9:5.6), and only the pH was varied.

[0094] Table 3. Effect of pH on Li and Al yields

[0095]

[0096] As can be seen from Table 3, the highest Li yield was obtained at pH 1.5.

[0097] in conclusion

[0098] In conventional lithium battery recycling methods, the lithium recovery process step occurs at the last step of the method. For example, when leaching the black mass with a suitable acid and leaching agent, impurities are removed in the pH range of 3-4, the metal of the battery is recovered at a pH of 4-6, and finally the lithium is recovered in the form of lithium carbonate, lithium phosphate or lithium hydroxide at a pH of >10. In this method, a large amount of lithium may be lost in the previous process steps, resulting in a lower lithium yield for the entire method.

[0099] The method described in this paper addresses this challenge by adjusting the stoichiometric ratio of Li:Al:F to precipitate lithium as cryolite at a pH as low as 1.5. Although lithium recovery can also be performed at higher pH, the risk of Fe, Ni, and Co co-precipitation increases at higher pH. Therefore, low pH is optimal for the selective recovery of Li from the black matter leach solution.

[0100] Since the solubility of lithium in the test area is in the range of 1100-1600 mg / l, the lithium recovery rate also depends on its initial concentration.

Claims

1. A device for recovering one or more metals including lithium from a leaching solution derived from lithium-containing spent batteries, the device comprising: - a pH adjustment unit (1) having an inlet for an initial leaching solution, an inlet for a pH adjustment reagent and an outlet for a pH adjusted leaching solution; - a reaction unit (2) for forming lithium cryolite, which has an inlet for an Al-containing reagent, a F-containing reagent and / or a Li-containing reagent, an inlet for a pH-adjusted leaching solution; and an outlet for a reaction mixture; the inlet for the pH-adjusted leaching solution of the reaction unit (2) is connected to the outlet for the pH-adjusted leaching solution of the pH adjustment unit (1); as well as - A recovery unit (3) for recovering lithium cryolite, the recovery unit (3) comprising an inlet for a reaction mixture from a reaction unit (2), an outlet for a lithium cryolite product and an outlet for a lithium-poor solution; the inlet for the reaction mixture from the reaction unit (2) of the recovery unit (3) is connected to the outlet of the reaction mixture of the reaction unit (2).

2. The device according to claim 1, wherein the pH adjustment unit (1) further comprises a pH control unit for controlling the pH of the pH-adjusted leaching solution to ≤4.

3. The device according to claim 1, wherein the pH adjustment unit (1) further comprises a pH control unit for controlling the pH of the pH-adjusted leaching solution to be 0.5-3.

4. The device according to claim 1, wherein the pH adjustment unit (1) further comprises a pH control unit for controlling the pH of the pH-adjusted leaching solution to be 1-2.

5. The device according to claim 1, wherein the pH adjustment unit (1) further comprises a pH control unit for controlling the pH of the pH-adjusted leaching solution to be 1.5-2.

5.

6. The device according to claim 1 or 2, wherein the reaction unit (2) further comprises a material control unit for making the Li:Al:F stoichiometric ratio of the reaction mixture in the reaction unit (2) be 3:0.8-2:4-8.

7. The device according to claim 1 or 2, wherein the reaction unit (2) further comprises a material control unit for making the Li:Al:F stoichiometric ratio of the reaction mixture in the reaction unit (2) be 3:0.9-1:4-7.

5.

8. The device according to claim 1 or 2, wherein the reaction unit (2) further comprises a material control unit for making the Li:Al:F stoichiometric ratio of the reaction mixture in the reaction unit (2) be 3:0.9:4.2-7.

2.

9. The device according to claim 1 or 2, wherein the recovery unit (3) further comprises a temperature control unit for making the temperature in the recovery unit (3) be 5 to 100°C.

10. The device according to claim 1 or 2, wherein the recovery unit (3) further comprises a temperature control unit for making the temperature in the recovery unit (3) be between 10 and 95°C.

11. The device according to claim 1 or 2, wherein the recovery unit (3) further comprises a temperature control unit for making the temperature in the recovery unit (3) be 20 to 80°C.

12. The device according to claim 1 or 2, wherein the recovery unit (3) further comprises a temperature control unit for making the temperature in the recovery unit (3) be between 25 and 70°C.

13. The device according to claim 1 or 2, wherein the recovery unit (3) further comprises a temperature control unit for making the temperature in the recovery unit (3) be 40 to 60°C.

14. The device according to claim 1 or 2, wherein the device further comprises a solid-liquid separation unit for separating lithium cryolite as a precipitate from the remaining solution. The device according to claim 14 , wherein the solid-liquid separation unit is a filtration unit.

16. The device according to claim 1 or 2, wherein the device further comprises one or more other separation units, which are arranged after the recovery unit (3) for separating one or more of the impurities Al, Fe and F from the remaining solution.

17. The apparatus according to claim 16, wherein the apparatus further comprises one or more metal recovery units, which are arranged after the one or more other separation units, for recovering one or more of the metals Ni, Co, Mn and Cu from the remaining solution.

18. The device according to claim 1 or 2, wherein the device further comprises one or more copper recovery units, which are arranged after the recovery unit (3) for recovering copper from the remaining solution.

19. The device according to claim 1 or 2, wherein the device further comprises one or more nickel and / or cobalt recovery units, which are arranged after the recovery unit (3) for recovering nickel and / or cobalt from the remaining solution.

20. The apparatus according to claim 1 or 2, wherein the apparatus further comprises one or more manganese recovery units, which are arranged after the recovery unit (3) for recovering manganese from the remaining solution.

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