METHOD FOR RECYCLING LITHIUM BATTERIES

Abstract

A method for recycling lithium batteries containing the steps: (a) digesting comminuted material (10), which contains comminuted components of electrodes of lithium batteries, using concentrated sulphuric acid (12) at a digestion temperature (T.sub.A) of at least 100° C., in particular at least 140° C., so that waste gas (14) and a digestion material (16) are produced, (b) discharging the waste gas (14) and (c) wet chemical extraction of at least one metallic component of the digestion material (16).

Claims

1. A method for recycling lithium batteries, comprising: (a) digesting a comminuted material containing comminuted components of electrodes of lithium batteries using concentrated sulphuric acid at a digestion temperature (T.sub.A) of at least 100° C., wherein digesting is performed such that a waste gas and a digestion material are produced, (b) discharging the waste gas, and (c) performing wet chemical extraction of at least one metallic component of the digestion material.

2. The method according to claim 1, wherein the digestion of the comminuted material comprises: (a) mixing the concentrated sulphuric acid and the comminuted material to produce a mixture, (b) detecting a mixture temperature (TM) of the mixture, and (c) controlling or regulating (i) a dosage mass flow (q.sub.m) of the concentrated sulphuric acid, and/or (ii) an addition mass flow (q.sub.10) of the comminuted material, so that the mixture temperature (T.sub.M) remains within a predetermined mixture temperature range (I).

3. The method according to claim 1, wherein the digestion of the comminuted material comprises: (a) dosing the concentrated sulphuric acid to the comminuted material with a dosage mass flow (q.sub.m) so that a mixture is created, (b) detecting a mixture temperature (T.sub.M) of the mixture, and (c) regulating the dosage mass flow (q.sub.m) so that the mixture temperature (T.sub.M) remains within a predetermined mixture temperature range (I).

4. The method according to claim 1 further comprising: (a) leaching a the digestion material, and conducting an ion exchange of the digestion material during which removes metallic impurities, wherein the ion exchange is performed prior to the wet chemical extraction of the at least one metallic component.

5. The method according to claim 1 further comprising conducting an ion exchange prior to performing the wet chemical extraction of the at least one metallic component wherein cobalt and/or nickel and/or manganese and/or lithium are not removed during the ion exchange.

6. The method according to claim 1 further comprising absorbing organic components prior to performing the wet chemical extraction of the at least one metallic component.

7. The method according to claim 1 further comprising: (a) separating, graphite from the digestion material thereby producing a raw fluid, and (b) purifying the graphite so that a content of non-metallic impurities is reduced compared to another content of non-metallic impurities if no purifying were performed.

8. The method according to claim 7, wherein purifying the graphite comprises a heating to a decomposition temperature (T.sub.Z) of a binder of 250° C. to 700° C.

9. The method according to claim 8, wherein the heating occurs (a) under an oxidizing atmosphere, (b) an inert atmosphere, or (c) a reducing atmosphere,

10. The method according to claim 7 further comprising: (a) classifying the graphite so that at least one fine fraction and at least one coarse fraction are obtained, wherein a binder content of binder in the at least one fine fraction is at least twice as large as in the coarse fraction, and/or (b) floating the graphite or the binder in an aqueous flotation fluid.

11. The method according to claim 7 wherein purifying the graphite comprises dissolving a binder out of the graphite using a solvent.

12. The method according to claim 7 wherein (a) purifying the graphite comprises a rinsing and/or washing with acid, and (b) purifying the graphite is carried out until a concentration of metallic impurities is at most 10 000 ppm.

13. The method according to claim 7 wherein (a) purifying the graphite comprises a leaching and/or washing with an oxidation agent, and (b) purifying the graphite is carried out until a concentration of metallic impurities is at most 10 000 ppm.

14. The method according to claim 1 further comprising separating graphite from the digestion material thereby producing a raw fluid; separating copper from the raw fluid so that a de-copperized raw fluid is obtained; and conducting an ion exchange after the copper has been separated.

15. The method according to claim 1 further comprising: (a) removing of cobalt from the digestion material by a cobalt complexing agent, and/or (b) removing nickel from the digestion material with a nickel complexing agent, and/or (c) removing manganese from the digestion material with a manganese complexing agent, so that a target fluid is obtained.

16. The method according to claim 1 wherein during wet chemical extraction (a) manganese is extracted before cobalt, and/or (b) cobalt is extracted before nickel.

17. The method according to claim 15 wherein removing nickel comprises a precipitation of alkaline nickel carbonate from a pure fluid obtained by precipitation of iron or aluminum from the digestion material.

18. The method according to claim 15 further comprising extracting lithium by solvent extraction from the target fluid.

19. The method according to claim 1 further comprising comminuting material prior to digesting and following comminution, heating the comminuted material to an electrolyte removal temperature (T.sub.E) of over 80° C. so that electrolyte in the comminuted material evaporates.

20. A recycling installation for processing lithium batteries, comprising: (a) a comminution unit for comminuting lithium batteries such that shredded material which contains components of electrodes of the lithium batteries is obtained, (b) a deactivation unit for deactivating the lithium batteries, (c) a reactor for digesting the shredded material with concentrated sulphuric acid at a digestion temperature (T.sub.A) of at least 100° C., (d) a sulphuric acid supply device for adding sulphuric acid to the shredded material, and (e) a discharge device arranged to discharge waste gas out of the reactor.

21. A recycling installation according to claim 20, further comprising: (a) a dosing device for dosing a dosage mass flow (q.sub.m) of the concentrated sulphuric acid to the shredded material so that a mixture is created, a mixture temperature detection device for detecting a mixture temperature (T.sub.M) of the mixture, wherein the dosing device is configured to regulate or control the dosage mass flow (q.sub.m), so that the mixture temperature (T.sub.M) remains within a predetermined mixture temperature range (I), and/or (b) a conveyor for adding the shredded material to the sulphuric acid, and a mixture temperature detection device for detecting a mixture temperature (T.sub.M) of the mixture, wherein the conveyor is configured to regulate or control an addition mass flow (q.sub.m), so that the mixture temperature (T.sub.M) remains within a predetermined mixture temperature range (I).

22. A recycling installation according to claim 21, further comprising: (a) a precipitation material separator for separating precipitated Cu or Cu compounds, and/or (b) a Fe/Al/Ti precipitation material separator for separating precipitated iron and/or aluminium and/or titanium compounds.

23. A recycling installation according to claim 21, further comprising a transition metal extraction device for (a) removing cobalt, and/or (b) removing nickel, and/or (c) removing manganese from a pure fluid so that a target fluid is obtained.

24. A recycling installation according to claim 23, further comprising a transition metal extraction device which comprises a solvent extraction device for (i) solvent extraction of cobalt, and/or (ii) solvent extraction of nickel, and/or (iii) removal of manganese by a manganese complexing agent.

25. The recycling installation according to claim 20 further comprising a graphite purification installation for reducing a content of binder on graphite which comprises (a) a classifier for classifying the graphite, so that at least one fine fraction and at least one coarse fraction are obtained, wherein a binder content of binder in the at least one fine fraction is at least twice as large as in the at least one coarse fraction, and/or (b) a washer for dissolving the binder out of the graphite using a solvent, and/or (c) a leaching reactor for purifying the graphite through rinsing and/or washing with acid and/or an oxidation agent.

Description

[0129] In the following, the invention will be explained in more detail by way of the attached figures. They show:

[0130] FIG. 1 a flow diagram of a method according to the invention and

[0131] FIG. 2 a schematic view of a recycling installation according to the invention,

[0132] FIG. 3 a flow diagram for a method according to the invention for processing comminuted material that is free of cobalt, nickel and manganese,

[0133] FIG. 4 the flow diagram of a method for processing comminuted material that is free of cobalt and nickel but contains manganese, and

[0134] FIG. 5 a flow diagram of a method according to the invention for comminuted material that is free of manganese and nickel but contains cobalt.

[0135] FIG. 6 a flow diagram for the processing of comminuted material that is free of manganese but contains cobalt and nickel.

[0136] FIG. 7 a schematic view of a recycling installation according to the invention.

[0137] FIGS. 8a and 8b show a flow diagram for a method according to the invention,

[0138] FIG. 9 shows a recycling installation according to the invention according to a further embodiment and

[0139] FIG. 10 schematically depicts a graphite purification installation of a recycling installation according to the invention.

[0140] FIG. 1 shows a flow diagram of a method according to the invention. First of all, the comminuted material, for example in the form of comminuted electrode active material, is provided. This may be achieved, for instance, using a method described in DE 10 2015 207 843 A1, which is incorporated with this reference. In particular, it is possible that batteries are initially comminuted, thereby resulting in raw comminuted material. In a subsequent step, the raw comminuted material is deactivated via drying, so that deactivated raw comminuted material is obtained.

[0141] The deactivation is preferably a drying. The drying occurs, for example, in an inert gas atmosphere or under a vacuum. It is favourable if a pressure is at most 300 hPa and a temperature during drying is at most 80° C. This results in comminuted material 10 that can no longer react electrochemically to a significant degree, as the proportion of low boilers in the electrolyte is too low.

[0142] After deactivation, the method may include the step of removing electrolyte. To this end, a container 11 is filled with the deactivated comminuted material 10 where it is heated to an electrolyte removal temperature T.sub.E of preferably above 100° C., especially above T=150° C. It is possible, but not necessary, that the container 11 is a vacuum container to which a vacuum of, for example, at least 300 hPa can be applied by means of a vacuum pump which is part of the recycling installation. In the container 11, electrolyte is removed from the comminuted material 10 that could not be removed during deactivation.

[0143] Deactivation and, where applicable, heating to the electrolyte removal temperature T.sub.E is followed by a separation of the electrode active material from the raw comminuted material according to a preferred embodiment of the method. This preferably comprises a combination of mechanical stress, magnetic separation, non-ferrous metal separation, sieving and density separation. It is practical to use air jet sieving, wherein the use of finer cut-sizes results in a purer sieved material.

[0144] The comminuted material 10 is mixed with sulphuric acid 12. The mixing may be, for instance, an agitation using an agitator. However, it is also possible that mixing is a simple addition. In particular, this is possible if the comminuted material 10 is in a reactor, for example in the form of a rotary kiln.

[0145] It is also possible that the comminuted material and the sulphuric acid are mixed in a reaction container. The resulting mixed comminuted material is then added to a reactor, especially a rotary kiln.

[0146] It is beneficial if the sulphuric acid 12 is dosed by means of a sulphuric acid supply device 43 (cf. FIG. 2). The preferred embodiments for this sulphuric acid supply device described in relation to FIG. 2 also apply for the method described in FIG. 1.

[0147] The sulphuric acid 12 is preferably at least 95%. The comminuted material 10 and the sulphuric acid 12 are brought up to a digestion temperature T.sub.A, for example at least T.sub.A=140° C., especially at least 150° C. Insofar as a pH value can be determined, it is below pH 1.5 for the mixture of comminuted material and sulphuric acid. In general, however, the water content of the mixture is too low to determine the pH value.

[0148] The digestion produces waste gas 14, which contains hydrogen fluoride HF in particular. The digestion occurs until a fluorine compound content, particularly a hydrogen fluoride content, in the waste gas 14 is below a predetermined threshold of, for instance, 0.83 mg per cubic meter, as determined in a discontinuous comparative test in a container without a continuous addition of material. This is checked using a fluoride detector 15, which continuously measures a fluoride concentration.

[0149] If digestion occurs in a charging process, the digestion is conducted until the fluorine compound content, especially a hydrogen fluoride content, is below a predetermined threshold of, for example, 0.83 mg per cubic meter.

[0150] Alternatively or additionally, digestion is conducted until a fluoride concentration c.sub.F of water-soluble fluoride in the digestion material is lower than 100 milligrams per kilogram of digestion material, preferably lower than 10 mg/kg and especially preferably below the traceability threshold. In other words, the retention time of the comminuted material 10 and the sulphuric acid 12 is selected in such a way that the digestion material has a fluoride concentration c.sub.F of water-soluble fluoride that does not exceed the specified values.

[0151] In addition, digestion material 16 is obtained that can be deemed, to a good approximation, to be fluoride-free. Water 18 is added to the digestion material 16, thereby leaching it. Leaching may occur in the same container in which the digestion of the comminuted material occurred; however, this is not essential. For instance, it is possible that the digestion material is put in a container that preferably already contains water. Leaching occurs at a pH value of −0.7 to 4 and preferably without an active addition or discharge of heat.

[0152] Following leaching, graphite 20 is separated using a graphite separation device 22. In the present case, the graphite separation device 22 is a filter with a pore size of at most 15 micrometers, preferably at most 10 micrometers. It is beneficial if the pore size is at least 0.5 micrometers.

[0153] The graphite 20 can be purified in a subsequent step in the method. This is achieved, for example, by adding water, an alcohol, an organic solvent or a mineral acid, so that electrode graphite is obtained. Electrode graphite is a graphite that is suitable for the production of electrodes, especially for lithium batteries. The separation of the graphite 20 results in a raw fluid 24.

[0154] The purification of the graphite 20 may comprise heating to a decomposition temperature T.sub.20 of T.sub.20> than 250° C., particularly T.sub.z>350° C. Preferably, T.sub.z<=430° C. Due to the heating, binder residues, for example made of polyvinylidene fluoride (PVFD), are decomposed. This preferably occurs in a sealed container.

[0155] Alternatively or additionally, purification may comprise a classification. However, classification is optional. The binder residues generally have a smaller diameter than the graphite particles, so that the binder residue content can be reduced by filtering out the smaller components.

[0156] Alternatively or additionally, purification may comprise a flotation. Flotation occurs in an aqueous fluid, for example.

[0157] If the purification includes the addition of a mineral acid, such as hydrofluoric acid or hydrochloric acid, the silicone content is also reduced, which is advantageous.

[0158] Metallic copper Cu is obtained from the raw fluid 24, for instance via cementation. To this end, metallic iron is brought into contact with the raw fluid 24, for example, so that iron ions dissolve and copper precipitates metallically.

[0159] Alternatively, the copper is separated in the form of copper sulphide. This is achieved, for instance, via precipitation by adding sodium hydrogensulphide NaHS.

[0160] The separation of the copper results in de-copperized raw fluid 26. This has a pH value between 0 and 4, for instance pH 1.

[0161] The Fe.sup.2+ ions in the de-copperized raw fluid 26 are then oxidized to form Fe.sup.3+ ions. In the present case, this is achieved by adding hydrogen peroxide H.sub.2O.sub.2. However, a different oxidation agent can also be used. The pH value of the de-copperized raw fluid is below 4.3 prior to oxidation. This step is preferably conducted without an active heat supply or extraction.

[0162] In a subsequent step, iron, aluminium and, where applicable, titanium are precipitated in the form of a hydroxide. To this end, the pH value is increased to a value between 4.3 and 8.7. This is achieved by adding sodium hydroxide and then separating, especially filtering out or centrifuging, the resulting precipitation. In addition to the separated hydroxides, a pure fluid 28 is also obtained.

[0163] It is possible, but not necessary, that the pure fluid 28 is purified of organic components by means of an activated carbon filter 27′. In particular, if purification has already been carried out beforehand, especially by means of activated carbon 27, this is unnecessary.

[0164] It is possible, but not necessary, that zinc and/or copper and/or iron and/or aluminium are removed by means of ion exchange. This is done with an ion exchanger 29. The stationary phase of the ion exchanger 29 is preferably a chelating agent with amino-phosphonic acid groups as functional groups.

[0165] Solvent extraction is used to extract nickel and cobalt from the pure fluid 28. In the present case, this is achieved using Cyanex 301, which is dissolved in an organic solvent, generally kerosene.

[0166] FIG. 1 shows that two solvent extraction steps are nested inside one another. First, cobalt and nickel are extracted using Cyanex 301, which is dissolved in kerosene. Stripping with acid, especially with hydrochloric acid or sulphuric acid, is used to obtain a solution 30 that contains nickel and cobalt. Following further separation using Cyanex 272, they are crystallized separately.

[0167] If a metal, such as manganese, is specifically named, as it is here or generally in the description, this generally refers to the metals in their elementary form and compounds contained in this metal; it generally also includes the metal ions. The statement that manganese, cobalt and nickel are extracted thus also means that manganese, cobalt and nickel ions and any compounds, and especially ions, containing manganese, cobalt and nickel are removed.

[0168] The extraction of cobalt and nickel results in a target fluid 32 that contains manganese. The pH value of the target fluid 32 may be between −0.7 and 10.5.

[0169] There are (at least) three options for the further processing of the target fluid 32. According to a first option, the manganese in the target fluid 32 that contains manganese is removed by solvent extraction. This may occur, for instance, using D2EHPA dissolved in kerosene.

[0170] According to a second and third option, the manganese is removed by precipitation, which may occur, for instance, by adding sodium hydroxide. According to a third option, precipitation may occur by adding sodium carbonate.

[0171] The removal of the manganese produces a target fluid 34. The most important component of this fluid is lithium ions. According to a first alternative, the lithium can be precipitated as phosphate. To this end, sodium phosphate, for example, is added to the target fluid 34.

[0172] According to a second alternative, lithium is precipitated from the target fluid 34 as carbonate. This is done, for example, using sodium carbonate. A favorable temperature is at most 30 Kelvin below the boiling point of the target fluid 34 and preferably above 50° C. As an option, the lithium carbonate is washed using water at 50-100° C., preferably 80-100° C., and/or ethanol.

[0173] It is beneficial if the precipitation is preceded by a concentration step, thereby increasing the concentration of lithium. Alternatively, the lithium may be precipitated as lithium phosphate; to this end, sodium phosphate can be added, for example. Concentration may occur, for instance, via reverse osmosis and/or evaporation.

[0174] According to the third alternative, the lithium is extracted by solvent extraction. Details can be found in the description of FIG. 8b. The components of a lithium solvent extraction installation 84 for conducting solvent extraction are therefore only schematically depicted.

[0175] FIG. 2 depicts a schematic view of a recycling installation 36 according to the invention for processing lithium batteries, in the present case in the form of comminuted material 10 produced from lithium batteries. Alternatively, it is also possible that electrode material that does not need to be comminuted is processed in the recycling installation. In the present case, the recycling installation 36 features a reactor 40, in which the comminuted material 10 is digested with sulphuric acid 12. The comminuted material 10 and the sulphuric acid 12 are mixed together with a mixer 42. The mixer 42 is an advantage but not essential. The reactor 40 may be a rotary kiln, but this is not necessary. In particular, the reactor 40 may be a container, as in the present case, which may feature a mixer.

[0176] The sulphuric acid 12 is added by means of a sulphuric acid supply device 43, which may refer, for instance, to a dosing device, comprising a sulphuric acid container 45 and a controllable valve 47. However, it is also possible that the sulphuric acid 12 is is poured in from a container.

[0177] It is possible that the reactor 40 is first filled with the comminuted material 10, for example by means of a conveyor. The sulphuric acid 12 is then dosed by means of the controllable valve 47. A mixture temperature detection device 41 detects whether a mixture temperature T.sub.M of the mixture 39 remains within a predetermined mixture temperature range I. For example, the mixture temperature detection device 41 is a thermometer. However, it is also possible that the mixture temperature detection device 41 comprises a camera and an evaluation unit so that a foam development of the mixture 39 can be detected quantitatively or qualitatively if foam development is a measure of the mixture temperature T.sub.M of the mixture 39.

[0178] If the mixture temperature T.sub.M leaves the mixture temperature range, a dosage mass flow q.sub.m of sulphuric acid is reduced by further or completely closing the valve 47. If the mixture temperature T.sub.M moves back into the mixture temperature range I, the valve 47 is opened (further).

[0179] Alternatively, the reactor 40 is filled with the sulphuric acid 12 and the comminuted material 10 then added, for example by means of a conveyor 37, such as a belt conveyor or screw conveyor. If the mixture temperature T.sub.M leaves the mixture temperature range, an addition mass flow q.sub.10 of the comminuted material 10 is reduced, particularly to zero. If the mixture temperature T.sub.M moves back into the mixture temperature range I, the addition mass flow q.sub.10 is increased.

[0180] As another alternative, the sulphuric acid 12 and the comminuted material 10 are added simultaneously. If the mixture temperature T.sub.M leaves the mixture temperature range, an addition mass flow q.sub.10 of the comminuted material 10 is reduced, either the dosage mass flow q.sub.m or the addition mass flow q.sub.10 or both are reduced, particularly to zero.

[0181] The recycling installation 36 has a discharge device 44 in the form of a waste gas pipe, which can be connected to a vacuum generator so that the waste gas 14 is suctioned out of the reactor 40. Alternatively, it is possible that the excess pressure in the reactor 40 pushes the waste gas 14 through the discharge device 44. The discharge device 44 may feature a washer for washing out hydrogen fluoride. For example, in this washer, the waste gas 14 is brought into contact with a calcium compound, for instance an aqueous solution that contains calcium ions, so that hydrogen fluoride in the waste gas 14 is washed out.

[0182] Of course, other methods for removing hydrogen fluoride from the waste gas 14 are conceivable. It is also possible that the waste gas 14 is added to a reactor by means of the discharge device 44, in which the hydrogen fluoride reacts, for example, with an organic substance. The fluoride concentration c.sub.F is identified using a fluoride detector 15.

[0183] A leaching device 46 is arranged behind the reactor 40 in the direction of material flow M, wherein the digestion material 16 is leached, for instance with water, in said leaching device.

[0184] A graphite recovery device 48 is arranged behind the leaching device 46 in the direction of material flow M, wherein said graphite recovery device only features the graphite separation device 22 in the form of a filter in the present case. An optional wash-out device for washing out adherent leaching solution from the graphite is not depicted. It is also possible to initially fill a transport container with the graphite and to conduct the washing-out of adherent leaching solution following transportation to another location.

[0185] The graphite recovery device 48 can comprise a graphite purification installation 49 that features a leaching reactor 51 and/or a furnace 53 and/or a classifier 55.

[0186] The leaching reactor 51 is designed to leach the graphite 20 with a mineral acid, especially hydrofluoric acid or hydrochloric acid.

[0187] The furnace 53 is designed to heat the graphite 20 to the decomposition temperature T.sub.z. The furnace 53 may be connected to a gas feed 57 that supplies an oxidizing gas, especially oxygen or air, when heating is to be done in an oxidizing atmosphere. If heating is to be done in a reducing atmosphere, the gas feed 57 supplies a reducing gas, such as hydrogen. If heating is to be done in an inert atmosphere, the gas feed 57 supplies a shielding gas, such as nitrogen or argon, or alternatively or additionally a vacuum installation is connected to the furnace 57 to apply a vacuum of preferably at least 300 hPa to the furnace.

[0188] The classifier 55 is designed to create at least a fine fraction and coarse fraction, wherein the binder content of binder in the fine fraction is greater than in the coarse fraction.

[0189] The graphite purification installation 49 can also feature a flotation device for floating the graphite, by means of which binder residue can be separated from the graphite 20. It is possible that the graphite purification installation 49 features one, two, three or four of the named components. The graphite purification installation 49 is also optional.

[0190] As described above for the embodiment according to FIG. 1, the recycling installation 36 may comprise the ion exchanger 29. Alternatively or additionally, the recovery installation 36 can feature one or two activated carbon filters 27, 27′.

[0191] A copper extractor 50 is arranged behind the graphite recovery device 48 in the direction of material flow. According to a first alternative, the copper extractor comprises a container 52 for cementing the copper following the addition of iron, especially in the form of sheet iron or iron filings, as well as a precipitation material separator 54 for separating selected copper compounds. The precipitation material separator 54 may be a filter, for example. The pore size of the filter is preferably smaller than 50 micrometers and at least 1 micrometer.

[0192] According to an alternative embodiment, the precipitation material separator is designed to separate copper sulphide and the container 52 is for the reaction of the raw fluid 24 with NaHS, so that copper sulphide precipitates.

[0193] An Fe/Al/Ti separator 56 is arranged behind the copper extractor 50 in the direction of the material flow, wherein an oxidation agent 58 is added to the de-copperized raw fluid 26 in said separator. This may occur in a first container 60.1. The resulting solution is then transferred, for example pumped, into a second container 60.2. In this second container 60.2, a hydroxide is added, in particular an alkaline hydroxide. For instance, sodium hydroxide is added. This results in the precipitation of aluminium, iron and, where applicable, titanium in the form of a hydroxide or a hydrated oxide. The precipitation is removed by means of a particle separator 62 arranged down-stream in the direction of material flow. The particle separator 62 is formed by a filter, for example, which may have a maximum pore size of 15 micrometers.

[0194] The resulting pure fluid 28 is added to a transition metal extraction device 63, in the present case a solvent extraction device 64, which features a Co/Ni solvent extraction device 66. This comprises a multitude of reaction containers 8.1, 38.2, . . . , which are connected to one another as shown in FIG. 2. The structure of a solvent extraction device is known from the prior art and will therefore not be explained in further detail. This produces the target fluid 32 containing manganese.

[0195] The target fluid 32 is added to a manganese solvent extraction device 70, which generates target fluid 34.

[0196] According to an alternative, the target fluid 32 containing manganese is added to a second precipitation reactor 72, in which the manganese is precipitated as manganese hydroxide following the addition of a hydroxide, especially an alkaline hydroxide such as sodium hydroxide.

[0197] According to a third alternative, the target fluid 32 containing manganese is added to a precipitation reactor 74. Following the addition of a carbonate, in particular following the addition of sodium carbonate, manganese is precipitated in the form of manganese carbonate or separated.

[0198] According to a first alternative, the lithium is precipitated in respective containers as carbonate by adding sodium carbonate or, according to a second alternative, as phosphate by adding sodium phosphate. It is possible that the recycling installation 36 comprises a concentrator 74 for removing water from the target fluid 34 to facilitate precipitation. According to the third alternative, the lithium is extracted by solvent extraction. Details can be found in the description of FIG. 8b.

[0199] It is possible, but not necessary, that the recovery installation 36 comprises a graphite purification installation 49. The graphite purification installation 49 may comprise the leaching reactor 51 and/or the furnace 53. As another alternative or in addition, the graphite purification installation 49 may comprise a classifier 55. This applies in general for all embodiments of the invention.

[0200] FIG. 3 shows a flow diagram for a method according to the invention for processing comminuted material and/or electrode material that is free of cobalt, nickel and manganese. It should be noted that the method corresponds to the method according to FIG. 1, wherein the steps related to the extraction of cobalt, nickel and manganese have been omitted. The activated carbon filters 27, 27′ are optional, as is the ion exchanger 29.

[0201] FIG. 4 shows a flow diagram for the processing of comminuted material and/or electrode material that is free of cobalt and nickel but contains manganese. For the extraction of manganese, only the variation with solvent extraction is depicted. The three alternatives shown in FIGS. 1 and 2 for the removal of the manganese are also possible for the method according to FIG. 4 and represent preferred embodiments. The three alternatives are precipitation as manganese carbonate, precipitation as manganese hydroxide and solvent extraction.

[0202] The alternatives to recovering the lithium are precipitation as lithium phosphate or as lithium carbonate.

[0203] The activated carbon filters 27, 27′ are optional, as is the ion exchanger 29.

[0204] FIG. 5 depicts the flow diagram of a method for processing electrode and/or comminuted material that is free of manganese and nickel but contains cobalt. The alternatives to recovering the lithium are precipitation as lithium phosphate or as lithium carbonate. The activated carbon filters 27, 27′ are optional, as is the ion exchanger 29.

[0205] FIG. 6 shows a flow diagram of a method according to the invention for electrode and/or comminuted material that is free of manganese but contains cobalt and nickel. The alternatives to recovering the lithium are precipitation as lithium phosphate or as lithium carbonate. The activated carbon filters 27, 27′ are optional, as is the ion exchanger 29.

[0206] FIG. 7 depicts a second embodiment of a recycling installation 36 according to the invention, wherein the components arranged behind the leaching device 46 in the direction of material flow have been omitted for the sake of clarity.

[0207] It can be recognized that the recycling installation 36 comprises a comminution unit 118 and a deactivation device 126. The deactivation device 126 is designed as a drying device.

[0208] Lithium batteries 110.1, 110.2, . . . , in particular battery systems made up of several battery modules or battery stacks, which are in turn made up of several battery cells, are initially discharged in a discharge unit 112. This is followed by the dismantling of the lithium batteries 110 at a dismantling station 114, if this is necessary because the battery systems cannot otherwise be delivered into the comminution unit 118 for geometric or gravimetric reasons. To this end, where appropriate, the battery systems are opened and dismantled to the point at which the modules and/or stacks can be individually removed. If required, the individual lithium battery cells can also be separated from the drive electronics.

[0209] The resulting sub-units (modules/stacks) and/or cells 116.1, 116.2, . . . are added to the comminution unit 118. For example, the comminution unit 118 may be a rotary shear with at least one rotor and at least one stator. The comminution unit 118 may also comprise a cutting mill with a rotor or several rotors.

[0210] The comminution unit 118 comminutes the lithium batteries 110.i under shielding gas 120, which is extracted, for example, from a shielding gas cylinder 122. Alternatively or additionally, liquid nitrogen from a liquid nitrogen source 119 may be may be injected. The shielding gas may refer, for example, to nitrogen, a noble gas, carbon dioxide, nitrous oxide or another gas which is preferably not toxic.

[0211] Shredded material 124 is produced during comminution, which is fed into a deactivation device in the form of a drying device 126. An airlock 128 is arranged between the comminution unit 118 and the drying device 126, the airlock being so gas-tight that the drying device 126 is—to a good approximation—separated from the comminution unit 118 so as to be gas-tight.

[0212] The drying device 126 is connected to a vacuum installation 129 that comprises a vacuum pump 130 and creates a vacuum. A pressure p.sub.126 from p.sub.126≈100±60 hPa, preferably 50 hPa, is present in the drying device 126. It should be noted that, within the scope of the present description, the vacuum pump should be understood particularly generally to mean a device that creates a vacuum. It is possible and preferred, but not necessary, for the vacuum pump to simultaneously work as a compressor, such that gas is emitted from it under a pressure that is greater than the ambient pressure.

[0213] In the case depicted in FIG. 7, the vacuum pump is a compressor which suctions in and compresses gas 131 that is present in the drying device 126. Alternatively or additionally, the vacuum installation 129 may have a jet pump, wherein a jet medium in the form of a liquid is directed at a high speed through at least one Venturi nozzle. The jet medium is preferably alkaline and has a pH value of at least pH 1 and is, for example, a 10% potassium hydroxide solution.

[0214] The vacuum installation 129 comprises a gas purification device 132 that is arranged between the drying device 126 and the vacuum pump 130, and which has a condenser 134 and/or an activated carbon filter 136 in the present case. The condenser is operated at a temperature of, for instance, −10° C. so that dimethyl carbonate and ethyl methyl carbonate condense and can be dispensed into a condensate container 138. In addition, any water present is separated by freezing. A control valve 140 is designed to open if the pressure p26 becomes too great and to close if the pressure p126 becomes too small, i.e. when a pre-determined threshold value is not reached.

[0215] The drying material is preferably moved in the drying device 126. This may be achieved by agitating with an agitator 141, such as an anchor agitator or a rod agitator with, for example, rods arranged perpendicular to the agitator shaft. Alternatively, it can be achieved by way of a drying container that is moved.

[0216] The drying of the shredded material 124 results in deactivated comminuted material 10, which is added to the mixer 42.

[0217] Alternatively, a transport container 146 is then filled with the deactivated comminuted material 10 under a vacuum and/or shielding gas. The transport container 146 is preferably gas-tight. It is possible, but not necessary, for the transport container 146 to be filled with inert gas prior to transportation so that it is under normal pressure. Alternatively, it is also possible for the transport container to be sealed under vacuum and transported. It is possible that, instead of the transport container, a vacuum-sealed foil is selected, such as an aluminium compound foil.

[0218] The comminution unit 118 is fed with shielding gas 120 from the vacuum pump 130 via a flushing line 148. If the vacuum pump 130 also functions as a compressor—as in the present case—which represents a preferred embodiment, the shielding gas 120 can be drawn from a pressurized gas cylinder 150. Alternatively or additionally, the shielding gas 120 can be given off into the surroundings, following additional purification if necessary.

[0219] FIG. 8a depicts multiple variations of a further method according to the invention. FIG. 8a shows that by extracting cobalt, nickel and silicon from the pure fluid 28, a target fluid containing manganese 32 is obtained.

[0220] According to a first alternative, manganese sulphate or manganese chloride are obtained from the target fluid containing manganese 32 through crystallization.

[0221] According to a second alternative, manganese carbonate is obtained through precipitation with a carbonate, such as sodium carbonate.

[0222] As a third alternative, manganese hydroxide is precipitated by adding sodium hydroxide, for example. A manganese-free target fluid 76 is produced from the target fluid containing manganese 32, from which cobalt is removed, for example using Cyanex 272. This results in a fluid containing cobalt 78, from which cobalt is crystallized in the form of cobalt sulphate or cobalt chloride. In addition to the fluid containing cobalt 78, a cobalt-free fluid 80 is produced, which contains nickel and lithium.

[0223] FIG. 8b shows the further processing of the cobalt-free fluid 80. First, nickel is extracted either according to a first alternative by solvent extraction and from the resulting fluid containing nickel 82 the nickel is crystallized as nickel sulphate or nickel chloride. Alternatively, nickel is precipitated, for example by adding sodium carbonate. From the resulting target fluid 34, lithium is precipitated as lithium carbonate according to a first alternative, as lithium phosphate according to a second alternative or, according to a third alternative, extracted by means of Cyanex 936, for example, and then precipitated as lithium carbonate.

[0224] FIG. 9 shows a recycling installation according to the invention according to a further embodiment.

[0225] FIG. 10 schematically depicts an embodiment of the graphite purification installation 49, which has a washer 86. The washer 86 features a container 88 in which the graphite 20 is mixed with a solvent 90. A temperature of the solvent 90, in the present case water with 10% by weight N-Methyl-pyrrolidone, is heated to T.sub.90=60° C. The mixture of solvent 90 and graphite 20 is mixed using a mixer. Solvent is withdrawn from the container 88 by means of a separator 92, the temperature is lowered so that the solubility of binder residues in the solvent is reduced, and the precipitated binder residues are separated, for example filtered off. The solvent 90 is then returned to the container 88.

TABLE-US-00001 Reference list 10 comminuted material 11 container 12 sulphuric acid 14 waste gas 15 fluoride detector 16 digestion material 18 water 20 graphite 22 graphite separation device 24 raw fluid 26 de-copperized raw fluid 27 activated charcoal filter 28 pure fluid 29 ion exchanger 30 solution 32 target fluid containing manganese 34 target fluid 36 recycling installation 37 conveyor 38 electrode material 39 mixture 40 reactor 41 mixture temperature detection device 42 mixer 43 sulphuric acid supply device 44 discharge device 45 sulphuric acid container 46 leaching device 47 controllable valve 48 graphite recovery device 49 graphite purification installation 50 copper extractor 51 leaching reactor 52 container 53 furnace 54 precipitation material separator 55 classifier 56 Fe/Al/Ti precipitation material separator 57 gas supply 58 oxidation agent 60 container 62 particle separator 63 transition metal extraction device 64 solvent extraction device 66 Co/Ni solvent extraction device 68 reaction container 70 Mn solvent extraction device 72 precipitation reactor 74 concentrator 76 manganese-free target fluid 78 target fluid containing cobalt 80 cobalt-free target fluid 82 target fluid containing nickel 84 lithium solvent extraction installation 86 washer 88 container 90 solvent 92 separator 110 lithium battery 114 dismantling station 116 cells 118 comminution unit 119 liquid nitrogen source 120 shielding gas 124 shredded material 126 drying device 128 airlock 129 vacuum installation 130 vacuum pump 131 gas 132 gas purification device 134 condenser 136 activated charcoal filter 138 condensate container 140 control valve 141 agitator 146 transport container 148 flushing line 150 pressurized gas cylinder c.sub.F fluoride concentration M direction of material flow q.sub.m dosage mass flow T.sub.A digestion temperature T.sub.Z decomposition temperature