Method for recovering alkali metal batteries and battery treatment system

Abstract

The invention relates to a method for recovering an alkali metal battery (12), in particular a Li battery or a Na battery, comprising: an active material; a carrier foil on which the active material is disposed; a binder that bonds the active material to the carrier foil; a liquid electrolyte; a conductive salt (38); the invention relates to a method for producing an alkali metal battery (12) comprising an active material, a carrier foil, and a binder, and a housing which encloses the active material, the carrier foil, and the binder, having a step of comminuting the alkali metal battery (12) such that a comminuted material containing a black substance (30), which contains the active material and the binder, is produced, having the following steps: washing the comminuted material with a washing solvent (36), the electrically conductive salt (38) is washed away without the binder being washed away, such that a low-conductivity salt comminuted material and a washing liquid (40) are obtained; regenerating the washing solvent (36) from the washing liquid (40), in particular by distillation; and washing the comminuted material with at least a portion of the regenerated washing solvent (36). The invention also relates to a battery production system for recovering alkali metal batteries (12), in particular Li or Na batteries.

Description

Technical Field

[0001] The present invention relates to a method for recycling alkali metal storage batteries, in particular Li storage batteries or Na storage batteries, which comprise: (a) active materials, in particular graphite or silicon; (b) a carrier foil on which the active materials are arranged; (c) an adhesive by which the active materials are bonded to the carrier foil; (d) an electrolyte, in particular a liquid electrolyte; and (e) a conductive salt. Preferably, the alkali metal storage battery also has a housing; however, it may also be without a housing. The method comprises the step of pulverizing the alkali metal storage battery to obtain a pulverized material which contains a black substance that contains the active materials and the adhesive.

[0002] According to a second aspect, the present invention relates to a storage battery treatment system for recycling alkali metal storage batteries, in particular Li storage batteries or Na storage batteries, which has (a) a pulverizing system for pulverizing the alkali metal storage batteries. Background Art

[0003] Alkali metal storage batteries are being used on a large scale and with increasing scale to provide energy for electricity consumers. In particular, alkali metal storage batteries are used as traction batteries for electric vehicles. The use frequency of electric vehicles is increasing, especially because they can reduce CO2 emissions during use. In order to reduce the carbon footprint of electric vehicles, it is desirable to process alkali metal batteries as efficiently and resource-conservingly as possible.

[0004] CN 103 825 064A describes a method of washing out the electrolyte in a complete storage battery. After distilling the electrolyte, a part of the distillate is used again to wash out the electrolyte. After removing the electrolyte, the housing is sawn open at the head end and the electrodes are removed. The electrodes are unfolded and separated into a positive electrode, a separator and a negative electrode. This type of process is complex and requires high demands on process engineering, especially when processing a large number of storage batteries with different configurations.

[0005] CN 110 380 150 describes a method of first dismantling the storage battery. Then the electrolyte is washed out with an organic solvent and an organosiloxane, and the resulting mixture is heated so that the conductive salt reacts with the organosiloxane and precipitates. This makes it more difficult to recycle the conductive salt.

[0006] CN 113 322 380 describes a method of discharging and pulverizing the storage battery. By filtration, the electrolyte is separated from the pulverized material, and lime water is added so that the fluorine component precipitates as calcium fluoride.

[0007] WO 2014 / 208597 A1 describes a method of washing out the electrolyte in a complete accumulator. The resulting solution is mixed with water or an acid and evaporated under vacuum so that the fluorine component is discharged as hydrogen fluoride. SUMMARY OF THE INVENTION

[0008] The object of the present invention is to improve the recycling of alkali metal accumulators.

[0009] The present invention achieves the above object by the method described in the technical field part, the method comprising the steps of: (ii) washing the comminuted material with a washing solvent so that the conductive salt is washed out while the binder is not washed out, obtaining a comminuted material with a low conductive salt and a washing liquid; (iii) regenerating the washing solvent from the washing liquid; and (iv) washing the comminuted material with at least a part of the regenerated washing solvent.

[0010] According to a second aspect, the present invention achieves the above object by the accumulator treatment system described in the technical field part, the accumulator treatment system having: (b) a washing device which is designed and arranged to wash at least one fraction of the comminuted material, in particular the black material, with a washing solvent, obtaining a comminuted material with a low conductive salt and a washing liquid; and (c) a regenerator which (i) is designed to automatically regenerate the washing solvent from the washing liquid; (ii) comprises a feed line which is connected to the washing device to guide the washing liquid from the washing device to the regenerator; and (iii) comprises a reflux line which is connected to the washing device to guide the washing solvent from the regenerator to the washing device.

[0011] The advantage of the present invention is that the conductive salt can generally be recovered on a large scale. The conductive salt recovered in this way can be reused in alkali metal accumulators. For this purpose, it may be advantageous to separate the conductive salt from the washing liquid or a part of the washing liquid. In addition, it may be advantageous to purify the conductive salt, for example, by crystallization and / or refining.

[0012] Preferably, the washing of the comminuted material and / or the regeneration of the washing solvent are carried out in such a way that at least 50 mol%, in particular at least 70 mol%, in particular at least 80 mol%, preferably at least 90 mol%, particularly preferably at least 95 mol% of at least one conductive salt and / or at least one anion of the conductive salt or at least one cation of the conductive salt remains unchanged and is in particular separated during regeneration. For example, it is preferred to add a very small amount of water and / or a very small amount of acid to the electrolyte and / or the comminuted material so that at least 80 mol%, preferably at least 90 mol%, particularly preferably at least 95 mol% of the conductive salt and / or the anion of the conductive salt remains unchanged.

[0013] Furthermore, it is advantageous that the method can generally be carried out in such a way that substantially no hydrogen fluoride is formed during the washing out of the conductive salt and / or during regeneration, and according to a preferred embodiment, the method is carried out in this way. Thus, according to a preferred embodiment, the fluorine bound in the conductive salt can be recovered to a large extent, preferably at least 95% by weight, in particular at least 97% by weight, particularly preferably at least 99% by weight.

[0014] The feature of substantially no hydrogen fluoride formation is specifically understood to mean that when washing out the conductive salt and / or during regeneration, at most 5 mol%, in particular at most 2 mol%, preferably at most 1 mol%, particularly preferably at most 0.1 mol%, particularly preferably at most 0.05 mol% of the fluorine in the alkali metal storage battery reacts to form hydrogen fluoride.

[0015] The electrolyte should be specifically understood to mean a solution composed of a conductive salt solvent and the conductive salt dissolved therein.

[0016] It is also beneficial that the electrolyte can often be recovered with a relatively high purity. It has been demonstrated that such pure electrolyte can be recovered and can be reused for the production of alkali metal storage batteries and can be used according to the preferred embodiment.

[0017] Within the scope of the description of the present invention, an alkali metal storage battery should be understood to mean a storage battery in which, during the release of electrical energy, an alkali metal, in particular sodium or lithium, or a compound of an alkali metal migrates from one electrode to another electrode. It is possible, but not necessary, for the oxidation and / or charge of the alkali metal to change during this process.

[0018] An alkali metal storage battery should also be specifically understood to mean an alkali metal rechargeable storage battery. A rechargeable storage battery means a storage battery that can be charged. In particular, a Li storage battery can also be understood to mean a rechargeable Li storage battery, i.e., a rechargeable storage battery.

[0019] Examples of alkali metal storage batteries are lithium-ion rechargeable storage batteries, such as lithium cobalt dioxide rechargeable storage batteries, lithium polymer rechargeable storage batteries, lithium manganese rechargeable storage batteries, lithium nickel cobalt manganese rechargeable storage batteries, lithium iron phosphate rechargeable storage batteries, lithium iron yttrium phosphate rechargeable storage batteries, lithium titanate rechargeable storage batteries, lithium metal polymer rechargeable storage batteries and lithium rechargeable storage batteries with metallic lithium, as well as lithium-air rechargeable storage batteries, lithium-sulfur rechargeable storage batteries, sodium nickel chloride high-temperature storage batteries, sodium-sulfur rechargeable storage batteries and sodium-ion rechargeable storage batteries.

[0020] The comminuted material should be understood to mean the material obtained by comminuting an alkali metal storage battery.

[0021] The black material particularly refers to the sorted material containing graphite and / or silicon in the comminuted material. In particular, the black material contains at least 30% by weight, especially at least 40% by weight, of graphite. The black material preferably contains at least 10% by weight of transition metals and / or their compounds. For example, the black material contains at least 5% by weight of nickel and / or 3% by weight of cobalt. However, this is not necessary. This weight indication refers to the weight of nickel or cobalt and corresponds to the proportion in weight percentage obtained when all nickel or cobalt atoms are present in elemental form (i.e., not in compound form).

[0022] Specifically, the black material is the material obtained by separating plastic particles, especially the comminuted housing and / or comminuted separator foil of an alkali metal battery, from the comminuted material. The separator foil especially refers to the foil that separates the anode from the cathode.

[0023] Washing the comminuted material should be understood to mean bringing the comminuted material or a sorted material of the comminuted material, especially the black material, into contact with a washing solvent in such a way that the conductive salt is at least partially dissolved by the washing solvent. Dissolving the conductive salt produces a washing liquid from the washing solvent.

[0024] In particular, the feature that the conductive salt is washed out means that at least a part, especially at least half (in mole percentage, especially at least 60 mole percentage, particularly preferably at least 70 mole percentage, particularly preferably at least 80 mole percentage, particularly preferably at least 90 mole percentage) of the anions of the conductive salt are removed.

[0025] Regenerating the washing solvent from the washing liquid should be particularly understood to mean treating the washing liquid in such a way that the washing liquid is obtained again. In particular, regeneration is equivalent to separating the conductive salt from the washing solvent.

[0026] The feature that the washing solvent is a component of the electrolyte should be particularly understood to mean that it is the same substance. Preferably, at least a part of the washing solvent is included in the alkali metal battery comminuted in the method beforehand. At the start of the method according to the invention, it is preferred to use the washing liquid that is not included in the alkali metal battery or that is included in the alkali metal battery but is recycled. During the method, the conductive salt solvent is washed out from the comminuted material and a part of it is regenerated into the washing solvent. Since the conductive salt solvent is preferably removed during regeneration, the ratio of the conductive salt solvent in the washing solvent continuously increases.

[0027] In other words, the comminuted material is preferably washed with the components of its own conductive salt solvent.

[0028] Comminution particularly refers to comminution in the sense of mechanical process engineering. In particular, comminution thus particularly refers to transforming the size distribution of an object into a finer size range. In particular, comminution is the irreversible reduction of the size of an object such as an alkali metal storage battery. In particular, comminution is the release of the material bonding of an object that does not occur along the joint. In particular, comminution is not disassembly.

[0029] Comminution is preferably: (a) pressure comminution, where the object is crushed between two tool surfaces; (b) impact comminution, where the object is placed on one tool surface and crushed by the impact of a second movable tool; (c) friction comminution, where the object is subjected to the pressure of two relatively moving tool surfaces; (d) cutting comminution, where the object is cut into two parts by at least two cutting edges; and / or (e) collision comminution, where the object is thrown against a wall, impacts a moving tool, or where two objects collide.

[0030] An advantage of comminution, particularly cutting comminution, is that the proportion of extremely small plastic particles formed during the comminution of the housing is relatively small. Preferably, cutting comminution is carried out in such a way that the weight proportion (count-based, i.e., particularly not in weight percentage) of plastic particles produced during the comminution of the housing that have a weight less than one-tenth of the median weight of the plastic particles produced during the comminution of the housing is at most one-third, particularly at most one-tenth, of the weight proportion of plastic particles produced during the comminution of the housing that have a weight greater than the median weight. Machining processes such as sawing produce many small plastic particles, which are often difficult to separate in subsequent processes.

[0031] It is preferred to use solid comminution tools for comminution. The advantage of this is that the degree of contamination of the comminuted material is lower. If a liquid comminution tool is used, such as water during water jet cutting, this causes contamination of the comminuted material.

[0032] Preferably, during comminution, at least half (by weight), particularly 90% by weight, of the electrodes are cut off.

[0033] Cutting off the electrodes usually mixes the separated substances in the storage battery, particularly the cathode and anode coatings. Surprisingly, it has been shown that the individual components can be separated to the extent that the mixing disadvantages can be tolerated.

[0034] Preferably, during comminution, at least half (by quantity), particularly at least 90%, of the carrier foil and / or separator foil are cut off, particularly cut through at least once. In practice, smaller carrier foil particles are more difficult to separate from the other components of the comminuted material.

[0035] In particular, the comminuted material contains particles of the comminuted electrode and the comminuted housing and / or the comminuted separator foil. The housing is a structure that surrounds the electrode and shields the surrounding environment. Preferably, the housing is comminuted using the same comminution system as the other components of the alkali metal storage battery and / or comminuted simultaneously with them. Preferably, the housing and the carrier foil are comminuted simultaneously, i.e., using the same tool and comminuted at the same time. In particular, the housing and the carrier foil are cut, wherein the housing and / or the separator foil and the carrier foil are cut during the cutting process.

[0036] Alternatively or additionally, regeneration can include, for example, separating the conductive salt by reducing the temperature.

[0037] The feature of washing the comminuted material with at least a portion of the regenerated washing solvent should be understood to mean that for the purpose of washing away the conductive salt, the regenerated washing solvent comes into contact with the comminuted material at least partially again. In other words, the washing solvent is at least partially recycled.

[0038] Preferably, the temperature of washing the comminuted material with the washing solvent is at most 80 °C, in particular at most 70 °C, preferably at most 60 °C, particularly preferably at most 55 °C, very particularly preferably at most 50 °C, very particularly preferably at most 45 °C, in particular at most 40 °C. Lower temperatures do slow down the rate of washing away the conductive salt, but they significantly reduce the decomposition of the conductive salt and / or the formation of hydrogen fluoride.

[0039] The electrolyte contains a conductive salt solvent for dissolving the conductive salt. The conductive salt solvent can be a pure substance. Alternatively, the conductive salt solvent is a mixture of at least two pure substances. The electrolyte also contains a conductive salt.

[0040] The electrolyte should be understood in particular to mean a liquid or solid containing ions, i.e., ions of the conductive salt.

[0041] The conductive salt should be understood to mean a compound composed of anions and cations and dissolved in the conductive salt solvent. In particular, the anion is an alkali metal anion that is released or absorbed from the cathode and / or released or absorbed by the anode during charging and discharging. It is possible that the alkali metal storage battery contains a plurality of substances acting as the conductive salt. In this case, the conductive salt refers to the totality of all these substances.

[0042] Preferably, the conductive salt solvent contains methyl ethyl carbonate, i.e., ethyl methyl carbonate (EMC); and / or dimethyl carbonate, i.e., dimethyl carbonate (DMC).

[0043] As expected according to a preferred embodiment, if the comminuted material is washed in a batch operation, it is preferred to wash the comminuted material at least twice, in particular at least three times, preferably at least four times, in particular at least five times, each time using a fresh washing solvent. Preferably, the washing is carried out at most 1000 times. It has been found that washing at least once often results in an unsatisfactory purity of the recovered graphite and / or conductive salt.

[0044] As expected according to an alternative preferred embodiment, if the comminuted material is washed continuously or semi - continuously, it is preferred to provide the washing solvent in such a way that, at the end of the washing, the concentration of the conductive salt in the washing solvent is as high as in the case where the comminuted material has been washed at least twice, in particular at least three times, preferably at least four times, in particular at least five times, each time using a fresh washing solvent in a batch operation.

[0045] According to a preferred embodiment, the method comprises the step of separating the black material from the residual fraction, in particular by classification or screening. Preferably, the obtained black material is washed with a washing solvent. Alternatively or additionally, the separation of the black material may also include froth flotation. Similarly, alternatively or additionally, the separation may include preparing a suspension and centrifuging the suspension. Since the black material should consist of as much graphite as possible and anodes are usually coated with graphite, which usually consists of particles smaller than the particles of the housing and / or carrier foil, screening, in particular air jet screening, has proven to be advantageous.

[0046] The step of separating the black material from the residual fraction is carried out on the comminuted material, in particular the dry comminuted material. The residual fraction is the material remaining after the black material has been separated. In particular, the residual fraction and the black material form the comminuted material, in particular the dry comminuted material. Preferably, the residual fraction contains particles of comminuted housing and / or comminuted separator foil and / or comminuted carrier foil.

[0047] Preferably, the black material is separated from the residual fraction in such a way that the weight proportion of plastic particles in the black material is at most one - fifth of the weight proportion of plastic in the residual fraction. Thus, when washing the comminuted material, in particular the black material, the washing solvent does not or hardly come into contact with the plastic, i.e. the plastic material or plastic paper. Plastic swelling and / or contamination of the washing solvent by plastic or plastic components, which would otherwise occur frequently, are avoided. During swelling, the plastic may become more viscous, which may make it more difficult to separate the black material from the plastic after washing.

[0048] In particular, separating the black material from the residual fraction comprises or is the separation of the black material from plastic particles. In particular, the plastic particles include particles produced by comminuting the housing of an alkali metal storage battery.

[0049] The separation of the shredded material, especially the black mass, from the washing solvent is carried out, for example, by filtration.

[0050] Accordingly, the present invention also encompasses a method, which comprises the following steps: (i) shredding an alkali metal storage battery to obtain a shredded material, the shredded material containing a black mass, the black mass comprising an active material and a binder; (ii) then separating the black mass from the shredded material, especially by classification or sieving; (iii) washing the black mass of the shredded material with a washing solvent such that the conductive salt is washed out while the binder is not washed out, thereby obtaining a black mass with a low conductive salt content and a washing liquid; (iv) regenerating the washing solvent from the washing liquid, especially by distillation; and (v) washing the black mass with at least a portion of the regenerated washing solvent. Thus, the conductive salt can generally be recovered in a particularly high purity. The preferred embodiments specified in this description also apply to the present invention. This method preferably further comprises the steps described for other methods according to the present invention.

[0051] Preferably, the washing solvent is a component of the electrolyte. Preferably, the washing solvent consists of one or more compounds that are components of the electrolyte, at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 85% by weight, especially preferably at least 95% by weight, particularly preferably at least 98% by weight.

[0052] It is advantageous if the washing solvent is at least substantially free of diluents. This particularly means that at most 20% by weight, especially at most 15% by weight, particularly preferably at most 10% by weight, preferably at most 5% by weight of the washing solvent consists of substances not included in the electrolyte of the alkali metal storage battery.

[0053] It is advantageous if the washing solvent is substantially not in contact with water. The feature that the washing solvent is substantially not in contact with water should particularly be understood to mean that there is no contact with water that results in a reaction of at least 5 mol%, especially greater than 1 mol%, particularly preferably greater than 0.1 mol% of the conductive salt. In particular, no water is added to the washing solvent.

[0054] It is advantageous if the washing solvent contains at least two different solvents. This achieves an increased solubility of the conductive salt.

[0055] Preferably, the washing solvent contains at least 5% by weight, especially at least 10% by weight, particularly preferably at least 15% by weight, especially at least 20% by weight, particularly preferably at least 25% by weight of a first pure substance (the first washing solvent pure substance) and at least 5% by weight, especially at least 10% by weight, particularly preferably at least 15% by weight, especially at least 20% by weight, particularly preferably at least 25% by weight of a second pure substance (the second washing solvent pure substance). The first pure substance is preferably ethyl methyl carbonate. The second pure substance is preferably dimethyl carbonate.

[0056] Preferably, the concentration of the main component of the washing solvent (measured in weight percentage) deviates by at most 10 times, especially at most 9 times, especially at most 8 times, especially at most 7 times, especially at most 6 times, especially at most 5 times, especially at most 4 times, especially at most 3 times, especially at most 2 times, compared to the concentration of the main component of the conductive salt solvent.

[0057] The factor is calculated by determining the maximum value among the quantities including the concentration of the main component of the washing solvent and the concentration of the main component of the conductive salt solvent. The factor is the quotient of the maximum value (as the numerator) and the minimum value of a given quantity (as the denominator). The main component is a pure substance that contains the largest proportion (in weight percentage) of the washing solvent or the conductive salt solvent.

[0058] The conductive salt solvent is optimized to dissolve the conductive salt as effectively as possible. Therefore, if the main component of the washing solvent corresponds as closely as possible to the main component of the conductive salt solvent, it can usually dissolve the conductive salt particularly effectively.

[0059] Preferably, the concentration of the second main component of the washing solvent (measured in weight percentage) deviates by at most 10 times, especially at most 9 times, especially at most 8 times, especially at most 7 times, especially at most 6 times, especially at most 5 times, especially at most 4 times, especially at most 3 times, especially at most 2 times, compared to the concentration of the second main component of the conductive salt solvent. The second main component is a pure substance that contains the second largest proportion (in weight percentage) of the washing solvent or the conductive salt solvent. This further improves the solubility of the conductive salt in the washing solvent.

[0060] Preferably, the washing solvent is selected in such a way that it does not react with the conductive salt during washing.

[0061] Preferably, the washing solvent is selected in such a way that it does not form a compound with lithium during washing.

[0062] Preferably, during the washing of the comminuted material, especially the black material, the comminuted material, especially the black material, is moved, for example agitated or rotated in a rotating drum.

[0063] The washing can be carried out continuously, discontinuously (i.e., in batch operation mode) or semi - continuously.

[0064] Preferably, the comminuted material, especially the black material, is washed until at least 70 wt%, especially at least 75 wt%, especially at least 80 wt%, especially at least 85 wt%, especially at least 90 wt%, especially at least 95 wt% of the conductive salt is removed.

[0065] For example, this can be determined by taking samples of the comminuted material, in particular the black substance, at regular intervals and determining the content of the conductive salt. For example, this can be achieved by means of nuclear magnetic resonance (NMR) measurements.

[0066] Alternatively, it is also possible to continuously monitor the concentration of the conductive salt in the washing liquid, for example by means of (NMR) measurements. This concentration follows an extraction curve that plots the concentration of the conductive salt against the total amount of the washing solvent used. The extraction curve is strictly monotonically decreasing. The measured values are adjusted using a parameterized model function (curve fitting), where the parameters of the model function are selected in such a way that the original concentration can be determined from them. This model function can be used to calculate the concentration at which a predetermined proportion of the conductive salt has been removed. If the measured value is less than this concentration, the washing is terminated.

[0067] Likewise, as an alternative method variant, a preliminary test can determine the frequency and / or duration with which the washing solvent must be added and discharged to remove a predetermined proportion of the conductive salt.

[0068] According to a preferred embodiment, the regeneration of the washing solvent includes distillation, in particular vacuum distillation of the washing liquid.

[0069] The vacuum distillation is carried out at a regeneration temperature. The regeneration temperature is preferably at most 100 °C, in particular at most 80 °C, in particular at most 70 °C, in particular at most 60 °C, in particular at most 55 °C, in particular at most 52 °C, in particular at most 50 °C, in particular at most 48 °C, in particular at most 45 °C.

[0070] Preferably, the regeneration of the washing solvent is carried out in such a way that at least 80 mol%, in particular at least 90 mol%, of the conductive salt, in particular lithium hexafluorophosphate and / or the anion of the conductive salt, does not decompose and / or does not undergo a chemical reaction.

[0071] In particular, calcium compounds are substantially not added, and / or fluorine does not precipitate as calcium fluoride. The feature that calcium compounds are substantially not added should be understood to particularly mean that at most 5 wt%, in particular at most 1 wt%, particularly preferably at most 0.1 wt% of calcium compounds are added to the washing solvent.

[0072] The regeneration of the washing solvent is preferably carried out in such a way that the conductive salt is recovered. Alternatively or additionally, the regeneration of the washing solvent is carried out in such a way that at least 80 mol%, in particular at least 85 mol%, particularly preferably at least 90 mol%, particularly preferably at least 95 mol% of the anions of the conductive salt are deposited in the compound in an unchanged manner. In other words, during regeneration, preferably a substance is deposited that contains the same anion as the conductive salt, but may, but does not have to, contain a different cation.

[0073] The regeneration temperature is the highest temperature reached at the point of contact with the conductive salt (dissolved or undissolved) in the vacuum still.

[0074] The pressure at which the vacuum distillation is carried out is preferably lower than the vapor pressure of the washing solvent at the regeneration temperature.

[0075] According to a preferred embodiment, the distillation pressure p is selected such that both ethyl methyl carbonate (EMC, ethyl methyl carbonate) and dimethyl carbonate (DMC, dimethyl carbonate) evaporate. 42 .

[0076] Preferably, the distillation pressure p is selected such that no substance evaporates, 42 wherein the boiling point of the substance at normal pressure (1013 hPa) is higher than the separation boiling point T. trenn . Substances with a boiling point corresponding to or lower than the separation boiling point T trenn are referred to as low boilers.

[0077] The separation boiling point T trenn is higher, the more components of the electrolyte in the alkali metal battery become part of the washing solvent. Preferably, the separation boiling point T is selected in such a way trenn that at most five components of the electrolyte, in particular at most four components, preferably at most three components, and especially at most two components evaporate.

[0078] Preferably, the separation boiling point T is selected in such a way trenn that at least one component of the electrolyte, in particular at least two components, preferably at least three components, and especially at least four components evaporate.

[0079] The components of the electrolyte are pure substances, and their proportion in the alkali metal battery electrolyte is at least 0.5 mol%.

[0080] Preferably, T trenn > 108 °C, for example T trenn = 110 °C.

[0081] The method preferably includes the step of separating the conductive salt from the washing liquid. A separation residue is formed during the regeneration of the washing solvent. If the regeneration still performs vacuum distillation, a distillation sump is formed. Preferably, the conductive salt is separated from the separation residue, in particular from the distillation sump. For example, the conductive salt is separated by crystallization.

[0082] It is advantageous if the separated conductive salt is used for the production of a new alkali metal battery.

[0083] Preferably, the washing solvent consists of one or more compounds which are components as electrolytes and which are at least 50% by weight. It is advantageous if the method comprises the step of removing the washing solvent from the washing solvent cycle for the washing solvent.

[0084] It is advantageous if the removed washing solvent is used for the production of new alkali metal storage batteries.

[0085] According to a preferred embodiment, the method comprises the step of grinding a low-conductivity salt comminuted material. For example, this can be carried out using a turbo grinder, an impact grinder or a ball mill. Preferably, the low-conductivity salt comminuted material still contains a foil component, in particular a part of the carrier foil and / or the metal foil component. Preferably, the low-conductivity salt comminuted material contains, immediately after comminution, at least one third by weight of the metal foil component in the comminuted material; in particular, all the metal foil components are still contained therein.

[0086] After grinding, it is preferably sieved to separate out the black material. The amount of black material is the fraction with the smallest particle size. Preferably, the foil component, in particular the copper foil and / or the aluminium foil component, is separated from the remaining fraction. For example, this can be achieved using a fluidised bed separator or a classifier. As described below, the binder is preferably dissolved out of the recovered black material by means of a binder solvent.

[0087] According to a preferred embodiment, the method comprises the step of removing, in particular dissolving out, the binder from the low-conductivity salt comminuted material, in particular the low-conductivity salt black material, using a binder solvent, thereby obtaining a low-binder comminuted material, in particular a low-binder black material. Specifically, the binder solvent is not the washing solvent. In order to be able to reuse the active material, in particular graphite, for the production of alkali metal storage batteries, the purity of the active material must be high. It has been shown that this purity is more easily achieved when the binder is dissolved out.

[0088] Although it is theoretically desirable to remove the binder completely, this is not possible in practice. Preferably, at least 50% by weight, in particular at least 60% by weight, in particular at least 70% by weight, in particular at least 80% by weight, in particular at least 90% by weight of the binder is removed. Preferably, at most 99% by weight of the binder is removed.

[0089] Alternatively, the binder solvent is a component of the conductive salt solvent. Although the conductive salt solvent does not dissolve the binder at the operating temperature, it has surprisingly been shown that the conductive salt solvent can dissolve the binder, in particular at elevated temperatures.

[0090] Alternatively or additionally, the method further comprises the step of dissolving out the solid electrolyte from the low-conductivity salt comminuted material, in particular the low-conductivity salt black material, using a solvent, thereby obtaining a low-conductivity salt comminuted product, in particular a low-conductivity salt black material.

[0091] The binder solvent is preferably acetone, γ-butyrolactone (GBL), diethyl carbonate (DEC), dimethylacetamide (DMA), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), 3-heptanone, 3-hexanone, methyl ethyl ketone (MEK), methyl ethyl ketone (MEK), methyl octanoate, supercritical carbon dioxide, or a mixture of two, three, four or more of the proposed compounds.

[0092] The binder is preferably dissolved using at least one diluent. The diluent is preferably γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), 3-heptanone or 3-octanone. The diluent is used in combination with the binder solvent to dissolve the binder. For example, the binder solvent and the diluent are mixed. However, it is not necessary to use a diluent.

[0093] The binder and / or the solid electrolyte are preferably dissolved out at a temperature of at least 70 °C, in particular at least 90 °C, in particular at least 110 °C, in particular at least 130 °C, in particular at least 150 °C, in particular at least 175 °C, in particular at least 200 °C, in particular at least 240 °C, in particular at least 260 °C, in particular at least 280 °C, in particular at least 290 °C.

[0094] This temperature is preferably below the boiling temperature of the binder solvent at the pressure used.

[0095] It is advantageous if the binder is dissolved out at a temperature that is at most 30 Kelvin, in particular at most 20 Kelvin, preferably at most 10 Kelvin below the boiling temperature of the binder solvent at the corresponding process pressure.

[0096] The binder is preferably dissolved out under overpressure, for example an overpressure of at least 100 hPa, in particular at least 200 hPa, at least 500 hPa, at least 1000 hPa, at least 2000 hPa, at least 3000 hPa. The overpressure is preferably at most 10 MPa. This overpressure is the process pressure.

[0097] Before the binder is dissolved out, the low-conductivity salt comminuted material, in particular the low-conductivity salt black material, is preferably not pyrometallurgically oxidized and / or not heated to a temperature above 300 °C, in particular not heated to a temperature above 250 °C.

[0098] Before the binder is dissolved out, the low-conductivity salt comminuted material, in particular the low-conductivity salt black material, is preferably not heated in a hydrogen atmosphere.

[0099] According to a preferred embodiment, the method comprises the step of post-washing the low-binder comminuted material, in particular the low-binder black material, with a post-washing solvent so that the binder solvent is washed off. The post-washing solvent is preferably an organic solvent. The boiling point of the post-washing solvent is preferably lower than that of the binder solvent, preferably lower than 100 °C, in particular lower than 90 °C, in particular lower than 80 °C, in particular lower than 70 °C under normal pressure. For example, the post-washing solvent is acetone.

[0100] The method preferably comprises the step of regenerating the post-washing solvent. For example, this can be carried out by distillation, in particular vacuum distillation. Due to the regeneration, the post-washing solvent is separated from the binder solvent and is preferably reused for post-washing.

[0101] The washing solvent preferably contains at most 5% by weight, preferably at most 3% by weight, particularly preferably at most 1% by weight of alkaline earth metal hydroxide, in particular substantially free of alkaline earth metal hydroxide. The feature that there is substantially no alkaline earth metal hydroxide should be particularly understood to mean that the amount of potentially present alkaline earth metal hydroxide can be neglected.

[0102] Preferably, the washing solvent is selected in such a way that at most 20 mol%, at most 10 mol%, particularly preferably at most 5 mol%, particularly preferably at most 1 mol% of lithium reacts during washing to become lithium hydroxide. Preferably, the washing solvent is selected in such a way that lithium hydroxide is not formed during washing.

[0103] Before the binder is leached out, the low-conductive salt comminuted material, in particular the low-conductive salt black material, is not digested, i.e., has not been treated with inorganic acid.

[0104] According to a preferred embodiment, the method comprises the step of separating, in particular classifying, the low-binder material, in particular the low-binder black material, so as to obtain a graphite fraction and a transition metal fraction, in which at least one transition metal is enriched compared to the graphite fraction.

[0105] However, it is not necessary to separate the low-binder comminuted material.

[0106] According to one embodiment, the method initially comprises step (i) according to claim 1, then pre-drying, then separating plastic particles, in particular particles of the comminuted housing and / or comminuted carrier foil, thus obtaining a black material, then performing step (ii), (iii), (iv) according to claim 1, and then optionally drying the black material and classifying the (optionally dried) black material.

[0107] In this case, it is preferred to carry out the drying in such a way that at least 70% by weight, in particular at least 80% by weight, particularly preferably at least 90% by weight, especially at least 95% by weight of the washing solvent contained in the black substance is removed.

[0108] Alternatively or additionally, the pre-drying is preferably carried out in such a way that at least 50% by weight, in particular at least 60% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight, especially preferably at least 90% by weight of the electrolyte and / or electrolyte solvent is removed.

[0109] Transition metals are to be understood as elements having an incomplete d subshell or forming ions with an incomplete d subshell. In particular, cobalt and / or nickel are enriched in the transition metal concentrate compared to the graphite concentrate, preferably with an enrichment factor of at least 3 (which means that the concentration of the corresponding transition metal in the transition metal concentrate is at least three times the concentration of the corresponding transition metal in the graphite concentrate), in particular an enrichment factor of 4, in particular an enrichment factor of 5, preferably an enrichment factor of 6.

[0110] It has been shown that a higher enrichment factor can be achieved particularly effectively when as much of the binder as possible is removed. The exact reason is not yet fully understood. It is assumed that the binder sticks the individual graphite particles to each other and to the particles containing the transition metal or transition metal salt, thus enabling separation.

[0111] The separation can also be or include flotation, in particular foam flotation. However, it has been shown that a higher enrichment factor can be achieved by classification.

[0112] The classification is preferably fine classification. It is advantageous if the fine classification is carried out with a fine classifier having a classification wheel. The classification wheel can also be called a sorting wheel (Klassierrad). The classification wheel has depressions, in particular slots. The net width of the depressions (in particular the slot width) is preferably at least 0.1 mm, in particular 1 mm and / or at most 25 mm, in particular at most 15 mm, particularly preferably at most 10 mm.

[0113] Preferably, the fine classification is designed to rotate the classification wheel at a rotational frequency of the classification wheel between 500 and 20,000 revolutions per second. The higher the rotational frequency of the classification wheel, the smaller the aerodynamic diameter of the removed concentrate.

[0114] Preferably, the depressions and the rotational frequency are selected in such a way that the graphite concentrate has a graphite concentrate - particle size distribution in which 80% by volume of the graphite has a particle size of less than 20 μm.

[0115] Alternatively or additionally, the indentation and rotation frequencies are selected in such a way that the transition metal fraction has a transition metal fraction particle size distribution in which 90% of the particles have a particle size below 35 μm, in particular below 30 μm. Preferably, at least 50% of the particles have a particle size below 25 μm, in particular below 20 μm. It has been shown that this achieves a particularly high enrichment factor. The particle size is determined according to DIN ISO 13320:2009.

[0116] According to a preferred embodiment, the method comprises the step of drying the low-conductive salt comminuted material, in particular the low-conductive salt black mass, after washing the comminuted material, in particular the black mass, with a washing solvent. The drying is preferably carried out at a temperature of at most 80 °C, in particular at most 70 °C, in particular at most 60 °C, in particular at most 50 °C, preferably at most 45 °C. This largely prevents the formation of hydrogen fluoride. The feature of largely preventing the formation of hydrogen fluoride should be particularly understood to mean that the concentration of hydrogen fluoride in the gas atmosphere during drying is at most 1 mg / m 3 。

[0117] Alternatively, the drying is carried out at a temperature above the boiling point of the washing solvent. This is advantageous when washing with the washing solvent until the content of the conductive salt is so low that at least substantially no hydrogen fluoride is formed during the subsequent drying. For example, the drying is carried out at a temperature of at least 80 °C, in particular at least 100 °C, in particular at least 120 °C.

[0118] Preferably, the method comprises the following steps: after drying, washing the low-conductive salt comminuted material, in particular the low-conductive salt black mass, with a second solvent, the boiling point of the second solvent being lower than the boiling point of the washing solvent. If the washing solvent comprises two or more components, the boiling point of the second solvent is preferably lower than all components of the washing solvent. Then preferably the comminuted material, in particular the black mass, treated in this way is redried.

[0119] After drying, in particular after pre-drying, the foil components, in particular plastic and / or metal foil elements and / or particles of the comminuted housing, are preferably separated out. In particular, this is carried out before the binder is dissolved out. Preferably, the separation is carried out in such a way that after the separation, the foil weight fraction of the foil components is at most one fifth of the foil weight fraction before the separation. Thus, when the binder is dissolved out, the binder solvent does not or hardly comes into contact with the plastic or metal foil.

[0120] Preferably, before the binder is dissolved out, the low-binder comminuted material, in particular the low-binder black mass, is dried. The drying is preferably carried out at a pressure of at most 300 hPa, in particular at most 10 hPa. Thus, the binder solvent is less contaminated.

[0121] It is advantageous if the graphite of the graphite separation product is used for the production of new alkali metal storage batteries.

[0122] It is advantageous if the method comprises the following steps: separating a foil portion from the comminuted material before washing the comminuted material. The resulting comminuted material can be referred to as low-foil comminuted material, which can be effectively washed with a washing solvent. The foil can be a carrier foil, in particular a plastic foil and / or a metal foil. For example, it refers to a part of a separator foil and / or an aluminum foil and / or a copper foil.

[0123] According to a preferred embodiment, the method comprises the following steps: after comminution, preferably after separating the foil portion or before separating the particles of the foil portion and / or the comminution housing and before washing the comminuted material, pre-drying the comminuted material. The pre-drying is preferably carried out in such a way that at least 50% by weight, in particular at least 60% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight, particularly preferably at least 90% by weight of the electrolyte and / or the electrolyte solution is removed. The pre-drying can generally be referred to as drying.

[0124] In particular, the method comprises the following steps: (a) drying the comminuted material to obtain a dried comminuted material; (b) separating plastic particles, in particular particles of the comminution housing and / or the comminution carrier foil and / or the comminution separator foil, from the dried comminuted material, thereby obtaining a black substance; wherein (c) washing the black substance with a washing solvent. The plastic particles are preferably not washed with the washing solvent. This prevents the washing solvent from being contaminated by components from the plastic. In addition, it prevents the swelling of the plastic particles.

[0125] Preferably, the pre-drying is carried out at a pressure of at most 300 hPa and / or at a temperature of at most 70 °C, in particular at most 60 °C, particularly at most 50 °C. Preferably, the pre-drying is carried out at a low temperature such that at most 5 mol%, in particular at most 1 mol%, of the fluorine in the comminuted material reacts to form hydrogen fluoride.

[0126] According to a preferred embodiment, the method comprises the following steps: before comminution, short-circuiting the storage battery until the regeneration battery voltage of at least 75% of the primary cells is at most 0.4 V, in particular at most 0.3 V, preferably at most 0.2 V, particularly preferably at most 0.15 V, particularly preferably at most 0.1 V, in particular 0.05 V.

[0127] Short-circuiting the storage battery means that the conductive salt can be recovered in particularly high purity. The reason why short-circuiting increases the purity of the recovered conductive salt is not yet fully clear. It is speculated that a regeneration battery voltage much higher than 0 V causes local heat generation during comminution, which may promote the decomposition of the conductive salt and / or the formation of hydrogen fluoride.

[0128] It should be noted that a separate deep discharge does not result in a regenerated battery voltage of at most 0.2 V. Deep discharge should be understood to mean consuming the current of the storage battery until its capacity is almost completely exhausted, especially below the discharge cut-off voltage. The discharge cut-off voltage can be, for example, 0.1 volts. After deep discharge, the energy content of the storage battery is very low: on the one hand, the battery voltage drops sharply, and on the other hand, the discharge current that can be achieved is very small. Therefore, the methods in the prior art only include deep discharge.

[0129] However, it has been shown that the energy content after deep discharge is high enough to be able to cause the formation of hydrogen fluoride. The amount of hydrogen fluoride formed during the comminution of a deep-discharged but not short-circuited storage battery is indeed relatively small, but it has been shown that even a very low degree of contamination of the decomposition products with the conductive salt can have a negative impact on the suitability of the conductive salt and / or the electrolyte for the production of new storage batteries.

[0130] The regenerated battery voltage refers to the battery voltage of the corresponding primary battery after a given regeneration time, during which the two poles of the storage battery are not electrically connected. The feature that the two poles of the storage battery are not electrically connected should be understood to mean that the two poles are insulated from each other, i.e., the resistance between the two poles is at least 1 megaohm. In other words, no electrical energy is consumed from the primary battery during the regeneration time. In particular, during the regeneration time, the two poles of the primary battery of the storage battery are not electrically connected.

[0131] During the regeneration time, the battery voltage increases. Even if the storage battery is discharged to the battery cut-off voltage, for example, below 0.2 V, for example, 0 V, this also results in a regenerated battery voltage greater than the battery cut-off voltage.

[0132] It has been determined that for the storage battery INR18650-25R from Samsung produced in February 2022, the battery voltage is 0 V after being short-circuited for 1 hour. The regenerated battery voltage is 1 V. After being short-circuited for 3 hours, the regenerated battery voltage is 0.8 V. After being short-circuited for 5 hours, the regenerated battery voltage is 0.6 V. After being short-circuited for 24 hours, the regenerated battery voltage is 0.2 V.

[0133] Short-circuiting the storage battery until the regenerated battery voltage is at most 0.2 V, especially at most 0.15 V, especially at most 0.1 V, can also be referred to as regenerationssicheres Kurzschlieβen. Therefore, it is advantageous not to short-circuit the storage battery before performing a regenerationssicheres Kurzschlieβen on it.

[0134] It is possible to determine whether a regenerative safety short circuit has occurred by storing the corresponding storage battery at 1013 hPa and 23 °C for the regeneration time without an external electrical load and especially without a short circuit, and then measuring the battery voltage. In other words, even if the storage battery is crushed or otherwise processed before the regeneration time has elapsed, a short circuit can be carried out such that at least 75% of the rechargeable storage batteries have a specified maximum regenerative battery voltage. The only determining factor is whether they are short-circuited such that the specified regenerative battery voltage is not exceeded after the regeneration time has elapsed.

[0135] The regeneration time is 12 hours. It should be noted that this is not a statement about the duration of the short circuit of the storage battery. Instead, the regeneration time is the time during which the storage battery is in a non-contact state, especially a non-short-circuit state, after discharging, especially short-circuiting. In particular, short-circuiting the storage battery for 12 hours may still result in a regenerative battery voltage higher than 0.2 volts.

[0136] Preferably, the short-circuit time of the short circuit of the storage battery is at least 8 hours, especially at least 10 hours, preferably at least 12 hours, especially at least 15 hours, especially at least 18 hours. If the short-circuit time is at least 20 hours, such as 24 hours, it is particularly advantageous. Preferably, the short-circuit time is less than 120 hours. As expected according to a preferred embodiment, this makes it possible to ensure that at least 90% by weight, especially at least 95% by weight, of the conductive salt of the storage battery does not decompose during crushing.

[0137] Preferably, the step before washing the black substance is carried out in such a way that at most 10% by weight, especially at most 5% by weight, especially at most 3% by weight, especially at most 1% by weight, especially at most 0.5% by weight, especially at most 0.1% by weight of the conductive salt of the alkali metal storage battery decomposes.

[0138] It is advantageous if a metal conductor is used for short-circuiting. In this process, the metal conductor connects the two poles of the storage battery, i.e., the negative pole and the positive pole. This means that the metal conductor does not connect the two poles of the storage battery to a resistor or another electrical consumer. It is particularly advantageous if the connection between the negative pole and the positive pole is not achieved by means of a liquid, especially a salt solution.

[0139] Preferably, the resistance between the positive pole and the negative pole of the storage battery during short-circuiting is at most 10 ohms, especially at most 1 ohm, preferably at most 0.3 ohm, and particularly preferably at most 0.1 ohm.

[0140] Optionally but not necessarily, the storage battery is transported after a regenerative safety short circuit, particularly over a distance of at least 1 km, particularly at least 5 km. The regenerative safety short circuit minimizes the fire risk and thus the environmental hazard posed by the storage battery. Preferably, after the regenerative safety short circuit, the storage battery is not transported over a distance of more than 1 km, as such transportation may pose a safety risk.

[0141] According to a preferred embodiment, the comminuted material is substantially not in contact with water before washing. The feature that the comminuted material is substantially not in contact with water should be particularly understood to mean that there is no contact with water that results in a reaction of the conductive salt of at least 5 mol%, particularly greater than 1 mol%, particularly preferably greater than 0.1 mol%. In particular, comminution is carried out without introducing water, particularly without water jet cutting.

[0142] Preferably, the comminuted material contains at least substantially no organic cations. This should be particularly understood to mean that the content of substances having organic cations is at most 0.1% by weight. Particularly preferably, the comminuted material does not contain any organic cations and / or no double-layer capacitors.

[0143] Preferably, before and during comminution, the active material and / or the electrolyte are substantially not in contact with water. This should be understood to mean that there is no contact with water that results in a reaction of more than 5 mol%, particularly more than 1 mol%, particularly more than 0.1 mol% of the conductive salt or electrolyte.

[0144] Preferably, before and during washing, the active material and / or the electrolyte are substantially not in contact with water. This should be understood to mean that there is no contact with water that results in a reaction of more than 5 mol%, particularly more than 1 mol%, particularly more than 0.1 mol% of the conductive salt or electrolyte.

[0145] Preferably, comminution is carried out at a low temperature such that, relative to the comminuted material, at most 2.5 mol%, particularly at most 1 mol%, particularly preferably at most 0.5 mol% of fluorine decomposes.

[0146] Preferably, the low-binder comminuted material, particularly the low-binder black material, is digested with concentrated sulfuric acid and then filtered off. Since it actually contains almost no binder, the amount of sulfuric acid used is very low. This makes it easy to obtain graphite with a low metal ion content. Then, if appropriate, the graphite can be reused for the production of alkali metal storage batteries.

[0147] The storage battery treatment system according to the present invention preferably includes a separation device that is designed and arranged to separate the black material from the residual sorting material. For example, the separation device is a classifier or a sieve.

[0148] Generally speaking, the present invention also includes the following method for recycling alkali metal storage batteries, in particular Li storage batteries or Na storage batteries, said storage batteries comprising:

[0149] (a) active material, in particular graphite

[0150] (b) carrier foil on which said active material is arranged,

[0151] (c) binder by which the active material is bonded to the carrier foil,

[0152] (d) liquid electrolyte,

[0153] (e) conductive salt and

[0154] (i) a housing which surrounds the active material, carrier foil and binder,

[0155] The method is characterized by the following steps

[0156] Optionally discharging and short-circuiting such that the regeneration voltage is below 0.2 V, in particular 0.1 V,

[0157] (ii) pulverizing the alkali metal storage battery to obtain a pulverized material comprising a black substance, active material and binder, and

[0158] (iii) optionally drying the pulverized material, in particular at a temperature below 70 °C and / or at a pressure of at most 300 hPa,

[0159] (iv) selectively separating the black substance, in particular by classification,

[0160] (v) washing the pulverized material, in particular the black substance, with a washing solvent such that the conductive salt is washed out while the binder is not washed out, thereby obtaining a pulverized material with low conductive salt content, in particular a black substance with low conductive salt content,

[0161] wherein the washing solvent is a component of the electrolyte,

[0162] wherein preferably the washing is carried out until at most 10 wt%, in particular at most 5 wt%, particularly preferably at most 1%, in particular at most 1 wt%, in particular at most 0.1%, in particular at most 0.1 wt%, in particular at most 1%, in particular at most 0.1% of the conductive salt remains,

[0163] recovering the washing solvent,

[0164] separating the conductive salt and / or substances having the same anion as the conductive salt from the residue formed during the recovery of the washing solvent,

[0165] At least one solvent is separated from the residue, which solvent is an electrolyte component rather than a washing solvent, and in particular is recovered for reuse in a new accumulator.

[0166] (vi) Optionally dry the low-conductivity salt comminuted material, in particular the low-conductivity salt black mass (which can be carried out at a temperature above the boiling temperature of the washing solvent, preferably below the binder decomposition temperature).

[0167] Optionally wash with a second washing solvent having a boiling point lower than that of the washing solvent.

[0168] (vii) Optionally dissolve the binder from the low-conductivity salt black mass with a binder solvent (which is not a washing solvent) to obtain a low-binder comminuted material.

[0169] (viii) Optionally dry the low-binder comminuted material, and

[0170] (ix) Optionally separate, in particular fractionate, the low-binder comminuted material to obtain a graphite fraction and a transition metal fraction, in which the transition metal fraction is enriched with at least one transition metal compared to the graphite fraction.

[0171] (x) Optionally produce a new accumulator, in particular an alkali metal accumulator, from the graphite and / or washing solvent and / or precipitated conductive salt of the graphite fraction.

[0172] The method preferably includes a step of washing out the binder solvent. For example, this is achieved using an organic solvent, which can also be referred to as a binder wash-out solvent. The boiling point of the binder wash-out solvent is preferably lower than that of the binder solvent. Preferably, the boiling point at normal pressure is lower than 100 °C, in particular lower than 90 °C, in particular lower than 80 °C, in particular lower than 70 °C, in particular lower than 60 °C.

[0173] In the accumulator treatment system according to the invention, the regenerator is preferably a vacuum still, which is designed to automatically distill the low-boiling fraction in the wash liquid, where the low-boiling fraction forms the wash liquid.

[0174] Preferably, the accumulator treatment system has a binder removal system, which is designed to automatically dissolve the binder in the low-conductivity salt comminuted material, in particular the low-conductivity salt black mass, with a binder solvent. The binder removal system is preferably arranged downstream of the washing device in the direction of the material flow. The dryer and / or separation device can be arranged upstream of the binder removal system in the direction of the material flow, but this is not necessary.

[0175] The binder removal system is preferably designed to heat the low-conductivity salt comminuted material, in particular the low-conductivity salt black mass, to a temperature above the binder decomposition temperature T BZ of. The binder decomposition temperature TBZ It refers to the temperature at which half of the adhesive decomposes after 30 minutes. This further reduces the adhesive residue, enabling a higher enrichment factor to be obtained in subsequent separation.

[0176] Preferably, the battery treatment system has an adhesive removal system, which is designed to automatically dissolve the adhesive from the comminuted material, especially the low-conductive salt, and particularly the black material of the low-conductive salt, by means of an adhesive solvent.

[0177] If an adhesive removal system is provided, the battery treatment system preferably has a post-washer, which is designed to wash the adhesive from the low-adhesive comminuted material, especially the low-adhesive black material, with a post-washing solvent. BRIEF DESCRIPTION OF THE DRAWINGS

[0178] Hereinafter, the present invention will be explained in more detail with reference to the drawings. Shown in the drawings are:

[0179] Figure 1 A flowchart of a battery treatment system according to the present invention.

[0180] Figure 2 A flowchart of a battery treatment system according to the present invention according to a second embodiment.

[0181] Figure 3 A flowchart of a battery treatment system according to the present invention according to a third embodiment.

[0182] Figure 4 A flowchart of a battery treatment system according to the present invention according to a fourth embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0183] Figure 1 A battery treatment system 10 according to the present invention is shown, which is used for recycling an alkali metal battery 12, which is lithium in the form of a lithium-ion rechargeable battery in the case of the present invention. First, the alkali metal battery 12 is preferably (but not necessarily) discharged by means of a discharging device 14. The electrical energy can be released into the power grid, such as the public power grid, but this is not necessary.

[0184] After discharging, the alkali metal battery 12 is preferably (but not necessarily) short-circuited. In other words, the positive electrode 16 and the negative electrode 18 are connected to each other. The resistance between the positive electrode 16 and the negative electrode 18 is preferably less than one-fifth, especially one-tenth, of the internal resistance of the corresponding alkali metal battery. The short circuit is carried out for a short-circuit time T K The short-circuit time T K is selected such that the regenerated battery voltage U reg is lower than U reg = 0.15V. For example, T s = 12 hours.

[0185] The alkali metal storage battery 12 is comminuted in the comminution system 22, thereby obtaining the comminuted material 22. The comminution system 20 is preferably designed in such a way that at most 5% by mass of the comminuted material 22 has a ball diameter greater than 4 cm. The ball diameter is the diameter of an imaginary sphere that completely surrounds the corresponding object.

[0186] The comminuted material 22 is guided via a pipeline 24.1 (preferably an airtight pipeline) to an optional separation device 26. An air lock 28.1 can be arranged in the direction of the material flow M between the comminution system 20 and the separation device. The separation device 26 separates the black material 30 from the residual sorting material 32. The residual sorting material 32 contains, for example, plastic components of the housing or diaphragm that may be provided.

[0187] The separation device 26 is depicted as a classifier, but it can also be (in general and not only in relation to the embodiment according to D1) a sieve system, a combination of a sieve system and a classifier, or a separation device based on another separation principle.

[0188] The black material 30 (or, in the absence of the separation device 26, the comminuted material 22) enters the washing device 34 via a pipeline 24.2 (preferably an airtight pipeline) and comes into contact with the washing solvent 36 in the washing device. The washing solvent 36 dissolves the conductive salt 38 from the black material 30, obtaining a washing liquid 40.

[0189] The washing liquid 40 enters a regenerator 42, which can be designed as a vacuum distiller, as in the case of the present invention. The term vacuum distillation device can also be used instead of vacuum distiller. The regenerator 42 includes a temperature control device 43 and separates at least the washing liquid 40 into a low-boiling sorting material (which is formed by the washing solvent 36) and a high-boiling sorting material 44.

[0190] The highest temperature at the point of contact with the conductive salt in the vacuum distiller 42 is called the regeneration temperature T r . Preferably, T r ≤ 60 °C, for example T r = 50 °C. The temperature control device 43 sets the regeneration temperature T r .

[0191] There is a distillation pressure p in the vacuum distiller 42 42 . The distillation pressure p is preferably selected in such a way that both ethyl methyl carbonate (EMC, ethyl methyl carbonate) and dimethyl carbonate (DMC, dimethyl carbonate) evaporate 42 .

[0192] Preferably, the distillation pressure p is selected in such a way that no substance evaporates 42 , the boiling point of which at normal pressure (1013 hPa) is higher than the separation boiling point T trenn. Preferably, T trenn > 108 °C, for example T trenn = 110 °C.

[0193] In this embodiment, the gaseous EMC and DMC are condensed by means of the condenser 46 and are led back as the washing solvent 36 into the washing device 34. Upstream of the condenser 46 in the direction of the gas flow, temperatures in the vicinity of the separation boiling point T trenn may be prevalent. It is advantageous to monitor this temperature using the thermometer 47.

[0194] A part of the washing solvent 36 can be extracted, for example, by means of the extraction line 48.1 and fed into the electrolyte container 50. Possibly after further processing, the washing solvent 36 can be used for the production of new alkali metal storage batteries.

[0195] The high-boiling fraction 44 containing the conductive salt remains in the vacuum still 42. The boiling points of the components of the high-boiling fraction 44 are higher than the separation boiling point T trenn . The high-boiling fraction 44 is extracted, for example, by means of the second extraction line 48.2 and can be fed into the transport container 52.

[0196] The distillation pressure p 42 is preferably below 286 hPa, in particular below 233 hPa, very particularly preferably below 188 hPa, in particular below 150 hPa.

[0197] In this embodiment, the low-boiling fraction contains substances with boiling points between 85 °C (in particular 88 °C) and 109 °C under normal pressure. If the alkali metal storage battery is a lithium-ion rechargeable battery, the low-boiling fraction particularly contains dimethyl carbonate and ethyl methyl carbonate.

[0198] In this embodiment, the low-boiling fraction 44 contains substances with boiling points above 110 °C under normal pressure.

[0199] In this embodiment, the washing device 34 operates in batch mode. The washing is carried out until the conductive salt in the washing liquid drops below a predetermined limit concentration c grenz . Then the black substance 30 is referred to as the low-conductive-salt black substance 30'. Preferably, the limit concentration c is selected in such a way that at least 95 wt% of the conductive salt is washed out of the black substance 30 grenz .

[0200] The low-conductive-salt black substance 30' enters the optional dryer 54 through the optional air lock 28.3. As in the case of the present invention, the dryer 54 can be designed as a vacuum dryer, but this is not necessary. For example, then in the dryer 54, the dryer pressure p 54 is generally p 54≤300 hPa. The dryer temperature T in the dryer 54 54 is preferably lower than T 54 = 60 °C. Thus, the washing solvent 36 in the low-conductive salt black substance 30' evaporates and condenses out in the condenser 56.

[0201] The dryer 54 preferably includes a mixer 57 to improve the contact between the washing solvent 36 and the black substance, and thus improve the outflow of the conductive salt and the electrolyte components that do not form the washing solvent 36.

[0202] The adhesive removal system 58 is arranged downstream of the washing device 34 along the direction of the material flow M, and in the case of the present invention, is arranged downstream of the dryer 54. The low-conductive salt black substance 30' enters the adhesive removal system 58 through the pipeline 24.4 (preferably an airtight pipeline) and, if applicable, through the air lock 28.4, and an adhesive solvent 60, such as dimethyl sulfoxide, is added thereto in the adhesive removal system.

[0203] As expected according to a preferred embodiment, if the adhesive solvent 60 contains supercritical carbon dioxide, the temperature and pressure in the adhesive removal system are selected in such a way that the carbon dioxide is supercritical.

[0204] Preferably, the adhesive removal temperature T in the adhesive removal system 58 58 is as high as possible, especially close to the boiling point T of the adhesive solvent 60 S,60 . Preferably, the adhesive removal temperature is at least T S,60 = 170 °C. Preferably, T S,60 = ≤ 400 °C, especially T S,60 = ≤ 375 °C. To achieve the highest possible adhesive removal temperature, it is advantageous if the process pressure p in the adhesive removal system 58 58 is greater than the ambient pressure. Preferably, p 58 ≥ 1200 hPa, especially p 58 ≥ 2000 hPa. In particular, p 58 ≤ 12 MPa.

[0205] The adhesive removal system 58 preferably has a stirrer 60 for introducing mechanical energy into the low-conductive salt black substance 30'. It is advantageous if the pH value in the adhesive removal system 58 is generally at most 9.

[0206] For example, the adhesive removal system 58 operates, for example, in a batch operation mode. The adhesive solvent 60 is replaced until at least 40%, preferably at least 50%, of the adhesive has been removed from the low-conductive salt black mass 30'. Subsequently, in the dryer 54.2, for example, by means of the pipeline 24.5, the resulting low-adhesive black mass 30" is dried. The temperature T in the second dryer 54.2 can be higher than the adhesive decomposition temperature T BZ , but it is not necessary. The generated exhaust gas 62 is purified by means of the exhaust gas purification system 64, especially hydrogen fluoride, and then released into the environment.

[0207] The low-adhesive black mass 30”' enters the separation device 66, which in the case of the present invention is designed as a fine classifier. The fine classifier 66 has a classification wheel 68, which reaches the classification wheel rotation frequency f by means of the electric motor 70 68 , for example f 68 = 150 1 / s.

[0208] The coarse fraction 74 leaves the fine classifier 66 through the coarse fraction outlet 72, and the fine fraction 78 leaves the fine classifier through the fine fraction outlet 76. The coarse fraction 74 contains significantly more graphite than the fine fraction 78, and therefore the coarse fraction can be called the graphite fraction. In contrast, the fine fraction 78 contains significantly more transition metals than the coarse fraction 74, and therefore the fine fraction can be called the transition metal fraction.

[0209] Figure 2 Shows a second embodiment of the battery treatment system according to the present invention, in which the vacuum distiller 42 is designed as a rectifier, i.e., a device for fractional distillation.

[0210] In this case, it is advantageous if the fraction with the lowest boiling point is used as the washing solvent or the weight percentage of the washing solvent 36 of the fraction is the highest.

[0211] Figure 3Shows a third embodiment of a battery treatment system 10 for recycling an alkali metal battery 12 (in particular a Li battery or a Na battery) according to the present invention, the battery treatment system having: (a) a comminution system 20 for comminuting the battery to obtain a comminuted material 22, the comminuted material containing a black substance 30, wherein the black substance particularly contains an active material and a binder; (b) a washing device 34 which is arranged downstream of the comminution system 20 in the direction of the material flow and is designed to wash at least one fraction of the comminuted material 22, in particular the black substance 30, with a washing solvent 36 to obtain a low-conductivity salt comminuted material 22 and a washing liquid 40; and (c) a regenerator 42 which (i) is designed to automatically regenerate the washing solvent 36 from the washing liquid 40; and includes (ii) a feed line which is connected to the washing device 34 for guiding the washing liquid 40 from the washing device 34 to the regenerator 42 and (iii) a return line which is connected to the washing device 34 for guiding the washing solvent 36 from the regenerator 42 to the washing device 34.

[0212] The battery treatment system 10 has a pre-dryer 80 which is arranged downstream of the comminution system 20 and upstream of the separation device 26 in the direction of the material flow M. In the pre-dryer, the pressure p54' is generally at most 300 hPa, for example p 54’ = 100 hPa. This low pressure (Unterdrück) is generated by a vacuum pump 82.

[0213] As an option, a condenser 56' can be arranged upstream (or alternatively, downstream) of the vacuum pump 82 in the direction of the gas flow G for condensing the conductive salt solvent 86. For example, the conductive salt solvent 84 can be used as the washing solvent 36 or used directly.

[0214] As an option, a particle filter 88 can be arranged upstream of the condenser 84 in the direction of the gas flow G. As an option, an activated carbon filter 90 can be arranged downstream of the vacuum pump 82 in the direction of the gas flow G. Then the gas purified in this way can be further purified or released directly into the environment.

[0215] The pre-dryer 80 can be connected to the separation device 26 by means of an air lock 28.5 and a pipeline 24.6 (preferably a particle-sealed pipeline).

[0216] In the separation device 26, the black substance 30 is separated from the residual fraction 32. The residual fraction particularly contains heavy materials, namely particles generated from the comminuted housing and the comminuted carrier foil and / or comminuted separator foil. The washing device 34 which washes the conductive salt out of the washing solvent 36 is arranged downstream of the separation device 26 in the direction of the material flow.

[0217] As an option, the battery handling system 10 may include a dryer 54, which is arranged downstream of the washing device 34 in the direction of the material flow.

[0218] As an option, the battery handling system 10 may include an adhesive removal system 58, which is arranged downstream of the washing device 34 (in particular the dryer 54, if provided) in the direction of the material flow.

[0219] If the battery handling system 10 has an adhesive removal system 58, it may include an optional post-washer 92, by means of which the adhesive solvent 60 is washed out of the low-adhesive black mass 30” using an adhesive wash-off solvent 94, thereby obtaining a wash solution 96. Preferably, the battery handling system has a wash solution regenerator 98 for separating the adhesive wash-off solvent 94 from the wash solution 96.

[0220] As an option, the battery handling system 10 has a classifier, in particular a fine classifier 66, to produce a graphite fraction and a transition metal fraction from the black mass 30”' (which may be a low-adhesive black mass).

[0221] As an option, the battery handling system 10 includes a discharging device 14.

[0222] The battery handling system 10 may include Figure 3 all of the components shown, but this is not necessary.

[0223] Figure 4 Another embodiment of a battery handling system 10 for recycling an alkali metal battery 12 (in particular a Li battery or a Na battery) according to the present invention is shown, the battery handling system having: (a) a comminution system 20 for comminuting the battery to obtain a comminuted material 22, the comminuted material containing a black mass 30, wherein the black mass particularly contains an active material and an adhesive; (b) a washing device 34, which is arranged downstream of the comminution system 20 in the direction of the material flow and is designed to wash at least one fraction of the comminuted material 22, in particular the black mass 30, with a washing solvent 36, thereby obtaining a low-conductive salt comminuted material 22 and a wash solution 40; and (c) a regenerator 42, which (i) is designed to automatically regenerate the washing solvent 36 from the wash solution 40; and includes (ii) a feed line, which is connected to the washing device 34 for guiding the wash solution 40 from the washing device 34 to the regenerator 42 and (iii) a reflux line, which is connected to the washing device 34 for guiding the washing solvent 36 from the regenerator 42 to the washing device 34.

[0224] Furthermore, the battery treatment system 10 has a dryer 54, which is arranged downstream of the washing device 34 in the direction of the material flow M. The dryer 54 can be a vacuum dryer, in which the process pressure p 54 is generally, for example, at most p 54 = 300 hPa, and / or the dryer temperature T 54 is generally, for example, at most T 54 = 70 °C. The preferred dryer temperatures described above also apply.

[0225] Alternatively, the dryer 54 can operate under normal pressure or overpressure, and / or at a dryer temperature T 54 above 70 °C, in particular above 80 °C, for example above 90 °C. For example, the dryer temperature is above the boiling temperature T S,36 of the washing solvent 36.

[0226] The separation device 26 that separates the black material from the residual sorting material 32 is arranged downstream of the dryer 54 in the direction of the material flow. The residual sorting material particularly contains heavy materials, namely particles generated by the crushed housing and the crushed carrier foil and / or the crushed separator foil.

[0227] As an option, the battery treatment system 10 includes an adhesive removal system 58, in which an adhesive solvent 60 is used to dissolve the adhesive in the black material 30. As an option, the battery treatment system 10 has another dryer 54.2 for drying the low-adhesive black material 30”.

[0228] If the battery treatment system 10 has an adhesive removal system 58, it can include an optional post-washer 92, by means of which the adhesive solvent 60 is washed out of the low-adhesive black material 30” using an adhesive wash-off solvent 94, thereby obtaining a wash solution 96. Preferably, the battery treatment system has a wash solution regenerator 98 for separating the adhesive wash-off solvent 94 from the wash solution 96.

[0229] As an option, the battery treatment system 10 has a classifier, in particular a fine classifier 66, to produce a graphite sorting material and a transition metal sorting material from the black material 30”' (possibly the low-adhesive black material).

[0230] The battery treatment system 10 can include Figure 4 all the components shown, but this is not necessary.

[0231] For example, the battery treatment system 10 does not have a dryer and / or a separation device downstream of the adhesive removal system 58 in the direction of the material flow.

[0232] List of reference numerals

[0233] 10 Battery processing system

[0234] 12 Alkaline metal battery

[0235] 14 Discharge device

[0236] 16 Positive electrode

[0237] 18 Negative electrode

[0238] 20 Crushing system

[0239] 22 Crushed material

[0240] 24 Pipeline

[0241] 26 Separation device

[0242] 28 Air lock

[0243] 30 Black substance

[0244] 32 Residual sorting material

[0245] 34 Washing device

[0246] 36 Washing solvent

[0247] 38 Conductive salt

[0248] 40 Wash liquor

[0249] 42 Regenerator

[0250] 43 Temperature control device

[0251] 44 High-boiling-point substance sorting material

[0252] 46 Condenser

[0253] 47 Thermometer

[0254] 48 Extraction pipeline

[0255] 50 Electrolyte container

[0256] 52 Transport container

[0257] 54, 54' Dryer

[0258] 56 Condenser

[0259] 57 Mixture

[0260] 58 Adhesive removal system

[0261] 60 Adhesive solvent

[0262] 62 Exhaust gas

[0263] 64 Exhaust gas purification system

[0264] 66 Fine classifier

[0265] 68 Classification wheel

[0266] 70 Motor

[0267] 72 Coarse separation product outlet

[0268] 74 Coarse separation product

[0269] 76 Fine separation product outlet

[0270] 78 Fine separation product

[0271] 82 Vacuum pump

[0272] 84 Condenser

[0273] 86 Conductive salt solvent

[0274] 88 Particle filter

[0275] 90 Activated carbon filter

[0276] 92 Post-washer

[0277] 94 Adhesive removal solvent

[0278] 96 Washing solution

[0279] c grenz Limit concentration

[0280] f 68 Classification wheel rotation frequency

[0281] G Direction of gas flow

[0282] M Direction of material flow

[0283] p 42 Distiller pressure

[0284] p 54 Process pressure

[0285] p 58 Process pressure in adhesive removal system

[0286] T S,36 Boiling point of washing solvent

[0287] T 54 Dryer temperature

[0288] T k Short-circuit time

[0289] T r Regeneration temperature

[0290] U reg Rechargeable battery voltage.

Claims

1. A method for recycling an alkali metal storage battery (12), in particular a Li storage battery or a Na storage battery, the alkali metal storage battery comprising: (a) an active material, (b) a carrier foil on which the active material is disposed, (c) an adhesive by which the active material is bonded to the carrier foil, (d) a liquid electrolyte, (e) a conductive salt (38) and (f) a housing that surrounds the active material, the carrier foil, and the adhesive, the method comprising the following steps: (i) comminuting the alkali metal storage battery (12) to obtain a comminuted material (30) containing a black substance that contains the active material and the adhesive, characterized by the following steps: (ii) washing the comminuted material with a washing solvent (36) such that the conductive salt (38) is washed out while the adhesive is not washed out, thereby obtaining a low-conductive-salt comminuted material and a washing liquid (40), (iii) regenerating the washing solvent (36) from the washing liquid (40), in particular by distillation, and (iv) washing the comminuted material with at least a portion of the regenerated washing solvent (36), (v) the washing solvent (36) being a component of the electrolyte.

2. The method according to claim 1, characterized by the following steps: after comminuting the alkali metal storage battery (12), separating the black substance (30) from the residual sorting material (32), in particular by classification or screening, wherein the black substance (30) is washed with the washing solvent (36).

3. The method according to any one of the preceding claims, characterized in that the concentration of the main component of the washing solvent of the washing solvent, measured in weight percentage, deviates by at most 10 times compared to the concentration of the main component of the conductive salt solvent of the conductive salt solvent.

4. The method according to any one of the preceding claims, characterized in that (a) the washing solvent (36) is substantially not in contact with water, and (b) the regeneration of the washing solvent (36) includes distilling and separating the conductive salt (38) from the washing liquid (40).

5. The method according to claim 4, characterized in that the regeneration of the washing solvent (36) includes vacuum distillation, the vacuum distillation At a regeneration temperature (T r ) of at most 70 °C and / or at a pressure below the vapor pressure of the washing solvent (36) at the regeneration temperature (T r ).

6. The method according to any one of the preceding claims, characterized by the following steps: (i) drying the comminuted material at a temperature of at most 60 °C and a pressure of at most 300 hPa, and (ii) separating the foil components, in particular plastic and / or metal foil components, before washing.

7. The method according to any one of the preceding claims, characterized by the following steps: after comminuting, preferably before or after separating the foil components and before washing the comminuted material, pre-drying the comminuted material, wherein the pre-drying is carried out in such a way that at least 50 wt% of the electrolyte solvent is removed.

8. The method according to any one of claims 1 to 6, characterized by the following steps: (a) Dry the comminuted material to obtain a dried comminuted material. (b) Separate plastic particles, in particular particles of comminuted housing and / or comminuted carrier foil, from the dried comminuted material to obtain the black substance. (c) Wash the black substance with the washing solvent (36).

9. The method according to any one of the preceding claims, characterized by the following steps: After washing the comminuted material, dissolve the binder from the low-conductive salt comminuted material with a binder solvent (60) to obtain a low-binder comminuted material.

10. The method according to any one of the preceding claims ， characterized by the following steps: (i) Separate, in particular finely classify, the comminuted material, in particular the low-binder comminuted material, to obtain a graphite fraction and a transition metal fraction, in which at least one transition metal is enriched compared to the graphite fraction.

11. The method according to any one of the preceding claims, characterized by the following steps: Before comminuting the accumulator, short-circuit the accumulator until the recovery cell voltage (U reg ) of at least 75% of the primary cells is at most 0.2 V, in particular at most 0.15 V.

12. The method according to any one of the preceding claims, characterized in that, the steps before washing the black substance (30) are carried out in such a way that the conductive salt (38) of the alkali metal storage battery (12) decomposes by at most 2% by weight.

13. The method according to any one of the preceding claims, characterized in that, (a) The comminuted material (22) is not in contact with water before washing, (b) The conductive salt (38) does not decompose, in particular is not in contact with water, not heated and does not react with the washing solvent (36), (c) The active material and / or electrolyte present in the alkali metal storage battery (12) are not in contact with water before and during comminution, (d) The alkali metal storage battery (12), the comminuted material and / or the black substance (30) are not subjected to pyrometallurgical treatment before washing, in particular heated to no more than 300 °C, and (e) The comminution is carried out at a low temperature such that, relative to the comminuted material (22), at most 2.5 mol% of fluorine decomposes.

14. A storage battery treatment system (10) for recycling an alkali metal storage battery (12), in particular a Li storage battery or a Na storage battery, the storage battery treatment system having: (a) A comminution system (20) for comminuting the storage battery to obtain a comminuted material (22), the comminuted material containing a black substance (30), the black substance containing an active material and a binder, (b) A washing device (34) designed and arranged to wash at least one fraction of the comminuted material (22), in particular the black substance (30), with a washing solvent (36) to obtain a low-conductive salt comminuted material (22) and a washing liquid (40), and (c) A regenerator (42) which (i) is designed to automatically regenerate the washing solvent (36) from the washing liquid (40), and (ii) including a feed pipeline that is connected to the washing device (34) for guiding the washing liquid (40) from the washing device (34) to the regenerator (42), and (iii) a reflux pipeline that is connected to the washing device (34) to guide the washing solvent (36) from the regenerator (42) to the washing device (34).

15. The battery processing system (10) according to claim 14, characterized in that the regenerator (42) is a vacuum distiller designed to automatically distill the low-boiling fraction in the washing liquid (40), wherein the low-boiling fraction forms the washing liquid (40).

16. The battery processing system (10) according to claim 14 or 15, characterized in that (a) a separation device (26) that is designed and arranged to separate the black material (30) from the residual fraction (32) and is arranged downstream of the comminution system (20) in the direction of the material flow (M), and / or (b) a dryer (54) that is arranged downstream of the washing device (34) in the direction of the material flow (M).

17. The battery processing system (10) according to claim 14 or 15, characterized in that a pre-dryer (80) that is arranged downstream of the comminution system (20) and upstream of the washing device (34) in the direction of the material flow (M).

18. The battery processing system (10) according to any one of claims 14 to 16, characterized in that an adhesive removal system (58) that is arranged downstream of the washing device (34) in the direction of the material flow (M) and is designed to automatically dissolve the adhesive from the low-conductivity salt comminuted material (22) by means of an adhesive solvent (60).

19. The battery processing system (10) according to any one of claims 14 to 18, characterized in that a classifier for classifying the low-adhesive black material to generate a graphite fraction and a transition metal fraction, in which at least one transition metal is enriched compared to the graphite fraction, wherein the classifier is a fine classifier (66) that includes a classification wheel (68).

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