Method for extracting residual lithium metal from group of one or more electrical energy storage cells

Abstract

The invention relates to a method for extracting residual lithium in a safe manner from a group of one or more electrical energy storage cells, in particular a battery, said group of electrical energy storage cells containing residual solid metallic lithium, and to a complete method for extracting lithium from a group of one or more electrical energy storage cells, in particular a battery, the present invention relates to a complete method for extracting residual lithium, the group of electrical energy storage cells comprising solid metallic lithium. The invention also relates to a device for extracting residual lithium implementing the method for extracting residual lithium.

Description

[0001] This invention relates to a method for safely extracting residual lithium from a component, particularly an electric battery, comprising residual solid lithium metal, and to a complete method for extracting lithium from a component, particularly an electric battery, comprising solid lithium metal, wherein the complete method implements the method for extracting residual lithium. The invention also relates to an apparatus for extracting residual lithium, implementing the method for extracting residual lithium.

[0002] The field of this invention is based on solid lithium metal batteries, particularly lithium-metal-polymer batteries, and even more particularly the field of recycling these batteries. Existing technology

[0003] Solid-state lithium metal batteries are known, such as lithium-metal-polymer batteries (LMP). ® These batteries are safer and have higher energy density, and are increasingly used in areas such as electric mobility and renewable energy storage. As a result, the number of solid-metal lithium batteries has been steadily increasing over the years, as has the number of end-of-life batteries. However, even at the end of their lifespan, the batteries still contain solid-metal lithium, which can be reused in other batteries or other applications and has considerable value.

[0004] The disposal of end-of-life lithium batteries is now a regulatory obligation. The new European battery regulations require that by 2026, at least 65% of the weight of batteries be recycled, and at least 50% of the lithium contained in these batteries be recovered.

[0005] Therefore, recycling the valuable metals contained in these batteries, especially lithium, has become economically attractive due to soaring prices. This price increase is driven by strong demand in the battery market for these transitional energy metals.

[0006] Against this backdrop, there are currently very few technologies for recovering metallic lithium from all-solid-state batteries (i.e., recovering lithium present in all-solid-state batteries, particularly in the negative electrode). These rare technologies specify heating the battery to a temperature greater than or equal to the melting temperature of metallic lithium to recover liquid lithium. Other technologies involve grinding the battery in a controlled atmosphere (CO2, Ar, etc.) or at low temperatures (e.g., -150°C) to prevent metallic lithium from reacting during the grinding process. However, these technologies pose a risk of battery fire, and from an industrial perspective, the processing conditions are expensive and limiting. Other methods for separating lithium ions from various metals (including lithium) present in the positive electrode active material of batteries have also been described. However, these methods are time-consuming and complex, and involve lithium-ion batteries with very different structures / materials and behaviors than metallic lithium batteries. In particular, the properties of metallic lithium in all-solid-state batteries differ from those of lithium ions in lithium-ion batteries.

[0007] A method for recovering lithium metal from an assembly comprising at least one battery cell containing solid lithium metal is known from international application WO2020 / 161339 A1. The method includes an extraction stage comprising the steps of: positioning the assembly with a first edge below a second edge opposite to the first edge, one or more negative electrodes protruding from the first edge of the assembly, and one or more positive electrodes protruding from the second edge of the assembly; and heating the assembly to a temperature greater than or equal to the melting temperature of the solid lithium metal, referred to as a processing temperature. Once the lithium metal melts, all or part of it is naturally expelled from each cell under gravity.

[0008] However, this solution is not entirely satisfactory because the extraction of metallic lithium is not optimized. In particular, the resulting batteries contain lithium residue that still adheres to the battery assembly at the end of the operation. Therefore, the battery cells produced by this method cannot be processed by conventional battery recycling methods, and the cathode contained in the cells cannot be recovered.

[0009] The purpose of this invention is to overcome this shortcoming.

[0010] Another object of the present invention is to provide a simple method for recovering residual solid lithium metal in a component of at least one energy storage cell.

[0011] Another object of the present invention is to provide an efficient method for recovering residual solid lithium metal in a component of at least one energy storage cell, while limiting and controlling the effects of potential short circuits during recovery.

[0012] Another object of the present invention is to provide a method for recovering residual solid lithium metal in a component of at least one energy storage cell, while ensuring the recycling of all or part of the liquids and solids used in the method. Summary of the Invention

[0013] The first object of the present invention is a method for extracting residual lithium from a component containing one or more residual solid lithium metal cells, the method comprising at least the following steps:

[0014] i) Immerse the component in an aqueous composition.

[0015] ii) Separating solids (and / or solid residues) from the aqueous composition,

[0016] iii) Adding at least one acid or its precursor, said acid or its precursor being capable of forming at least one lithium salt insoluble in the aqueous composition, and

[0017] iv) Recover lithium salts.

[0018] According to the method of the present invention, residual solid lithium metal is recovered from a component of one or more energy storage cells by processing one or more cells of the component individually or together.

[0019] In this invention, "solid lithium metal" or "solid lithium metal" refers to solid lithium in a zero oxidation state.

[0020] Furthermore, according to the method of the present invention, residual solid lithium metal from the component is recovered in the form of at least one salt by immersing the component in an aqueous composition to dissolve residual solid lithium metal, and then reacting the dissolved lithium with an acid to form a salt insoluble in the aqueous composition, which can then be easily recovered.

[0021] Therefore, the method according to the invention allows for the simple and uncomplicated recovery of residual solid lithium metal.

[0022] In addition, the method according to the invention provides for the reuse of the aqueous composition in one or more subsequent closed-loop residual solid lithium metal recovery processes.

[0023] In this application, each energy storage cell of a component consisting of one or more individual cells preferably contains residual solid lithium metal.

[0024] In this application, the statement "each cell contains residual solid lithium metal" means that each energy storage cell implemented in step i) is at least partially delithiated.

[0025] According to the preferred embodiment, each energy storage cell includes:

[0026] - Residual solid lithium metal, in the form of layers and / or debris, particularly from the negative electrode.

[0027] - Positive electrode, especially in layered form,

[0028] - A solid electrolyte or quasi-solid electrolyte containing lithium salt, particularly a layered solid electrolyte or quasi-solid electrolyte disposed on one side of the positive electrode, and

[0029] - A current collector associated with and / or located on one side of the positive electrode.

[0030] In other words, the component preferably includes residual solid lithium metal (from the negative electrode of multiple films or layers), as well as a solid electrolyte or quasi-solid electrolyte of multiple films or layers, a positive electrode, and a current collector.

[0031] In this application, "residual solid lithium metal" may include: residual pure lithium metal; or at least one residual lithium metal alloy; or a combination of residual pure lithium metal and at least one residual lithium metal alloy.

[0032] The components implemented in step i) may include a single or unique energy storage unit or multiple energy storage units.

[0033] When the component comprises multiple units (e.g., at least two units), they are preferably assembled along an assembly direction, or in particular stacked. The assembly direction may be perpendicular to the plane formed by each energy storage unit.

[0034] The component implemented in step i) is preferably a storage battery, and particularly preferably a storage battery in which multiple cells are connected in series.

[0035] The component used in step i) contains residual solid lithium metal. According to a preferred embodiment of the invention, the residual solid lithium metal in the component of one or more monomers implemented in step i) accounts for at most 20% by mass, preferably at most 15% by mass, and particularly preferably at most about 10% by mass, relative to the total mass of solid lithium metal present in the component of one or more monomers that is not delithiated.

[0036] Step i): Immerse the component in the aqueous composition.

[0037] This step dissolves the residual solid lithium metal in the aqueous composition. This is also known as the residual solid lithium metal dissolution step.

[0038] The entire assembly is immersed in the aqueous composition. In other words, the amount of aqueous composition is such that it completely covers the assembly. When the assembly comprises multiple energy storage cells, all cells are preferably immersed in the aqueous composition.

[0039] The aqueous composition preferably contains at least 90% by weight of water relative to the total weight of the aqueous composition, and particularly preferably at least 95% by weight of water. More particularly preferably, the aqueous composition consists of water alone.

[0040] The aqueous composition prior to immersion (i.e., before step i) preferably has a neutral pH, i.e., 6.5 to 7.5, and particularly preferably close to 7.

[0041] Step i) can be performed using a container or soaking tank containing an aqueous composition. In step i), the assembly of one or more energy storage cells is then placed in the soaking tank or container and covered with the aqueous composition.

[0042] Step i) preferably takes at least 30 minutes, and more preferably 1 to 2 hours. The duration of step i) will depend on the amount and / or size of the monomers in the component, and particularly on the presence or absence of a pre-treatment monomer cutting and / or grinding step as described below. Reduced monomer size in the aqueous composition facilitates dissolution.

[0043] The method may also include stirring the aqueous composition during step i). This improves the delithiation kinetics. Mechanical stirring may also be used. Step i) can be performed using one or more stirring devices, such as a shaft equipped with a mechanical stirrer.

[0044] The method may further include heating the aqueous composition during step i). This improves the delithiation kinetics. Step i) can be carried out using one or more heating devices, such as a reactor equipped with a double-walled jacket through which fluid circulates to heat the aqueous composition. Heating can be carried out at a temperature of about 40°C to about 70°C. Heating can begin before the component is immersed, i.e., before step i).

[0045] Step i) preferably results in the delamination of one or more membranes / layers of the solid electrolyte or quasi-solid electrolyte, the positive electrode, and the current collector. In other words, step i) also allows for the delamination of layers or membranes of individual monomers forming the component. In this way, layers or membranes of individual monomers forming the component are separated in step i).

[0046] Step ii): Solid / liquid separation

[0047] Between step i) and step iii), the method includes step ii) for separating solids (and / or solid residues) from the aqueous composition. Step ii) avoids excessive consumption of acid in the subsequent step iii). Furthermore, at the end of step i), the monomeric cathode is insoluble in the aqueous composition and must be separated from the aqueous composition before step iii) to prevent cathode residues from contaminating the lithium salt and complicating lithium salt recovery in step iv).

[0048] In step ii), solids (and / or solid residues) are separated from the aqueous composition, particularly by removing or discharging the solids (and / or solid residues) from the soaking tank or container. Step ii) may be carried out using one or more devices for separating solids and / or solid residues from the aqueous composition, such as filtration using a filter press or centrifugation using a centrifuge.

[0049] Step ii) may include or follow step ii'): washing the solids (and / or solid residues), preferably with water. Washing ii') is preferably carried out over the aqueous composition, particularly over an immersion tank or container. This increases the yield of lithium salts recovered by the method. Alternatively, washing step ii') can be carried out by injecting clean water during filtration, particularly in a filter press. Therefore, step ii') can be carried out simultaneously with step ii).

[0050] In practice, at the end of step i), the aqueous composition contains particulate and / or solid elements insoluble in the aqueous composition (referred to as solids and / or solid residues) (positive electrode active material, current collector, etc.). These solids are then removed in step ii). These solids are preferably positive electrode active material and / or current collector. In other words, in step ii), at least the positive electrode active material and / or current collector (also referred to as "black lumps") are separated from the aqueous composition as solids. The resulting aqueous composition then contains dissolved residual lithium and optionally one or more polymers of dissolved electrolyte.

[0051] Therefore, step ii) (and if step ii') provides a solid-free aqueous composition and ensures that all residual lithium is present in the aqueous composition.

[0052] Step iii): Add at least one acid or its precursor, said acid or its precursor being capable of forming at least one lithium salt insoluble in the aqueous composition.

[0053] Step iii) involves reacting the residual solid lithium metal dissolved in the aqueous composition with the acid to form a lithium salt insoluble in the aqueous composition. Therefore, step iii) facilitates the subsequent lithium salt recovery step iv).

[0054] Preferably, the acid or one of its precursors is selected from inorganic acids, such as phosphoric acid or carbonic acid, carboxylic acids, such as acetic acid, and mixtures thereof.

[0055] In step i), immersing the component in the aqueous composition results in the dissolution of lithium and an increase in the pH of the aqueous composition (potentially reaching a pH greater than or equal to 13). In step iii), the pH of the aqueous composition is decreased. Preferably, one of the acid or its precursor is added in an amount sufficient to precipitate all lithium present in the aqueous composition.

[0056] According to a preferred embodiment of the invention, the aqueous composition at the end of step iii) has a neutral pH, i.e., 6.4 to 7.6, and particularly preferably 6.5 to 7.5, and even more particularly preferably close to 7. This allows the aqueous composition to be reused to soak components with new monomers. Therefore, the aqueous composition can be used in a closed-loop manner.

[0057] In step iii), the aqueous composition is analyzed, for example, by ICP-AES, to measure the mass concentration of Li (in g / L). The mass concentration of Li in the aqueous composition is adjusted. It can be from 2 g / L to 30 g / L (depending on the amount of monomer impregnated), and is preferably from 5 g / L to 20 g / L.

[0058] The acid or its precursor is added to the aqueous composition at a rate of at least 10 g / L of the aqueous composition, and particularly preferably at a rate of 10 g / L to 500 g / L of the aqueous composition (depending on the acid used).

[0059] Step iii) preferably lasts for at least 10 minutes, and more preferably from 10 minutes to 60 minutes. The duration of step iii) will depend on the amount of residual lithium to be reacted with the acid or its precursor, the acid used, the volume of the aqueous composition, and / or the temperature of the mixture.

[0060] The method may further include stirring the aqueous composition during step iii). This improves the kinetics of lithium salt formation. Mechanical stirring may also be used. The stirring equipment may be those described in step i).

[0061] The method may further include heating the aqueous composition during step iii). This improves lithium salt formation kinetics and salt recovery yield. Heating can begin before the addition of the acid or its precursor, i.e., before step iii). Heating can be carried out using a reactor as described in step i) above. In particular, heating reduces the solubility of the Li salt in the aqueous composition, thereby increasing the recovery yield of dissolved Li.

[0062] Heating can be carried out at a temperature of about 50°C to about 100°C, and preferably at a temperature of 70°C to 90°C.

[0063] At the end of step iii), the aqueous composition contains at least one lithium salt that is insoluble therein. In other words, the lithium salt exists in the aqueous composition in solid form (i.e., as solid particles dispersed in the aqueous composition). The solid appearance can be detected visually or by spectroscopic methods such as UV-Vis absorption.

[0064] Step iv): Recover one or more lithium salts

[0065] Step iv) can be performed by filtration or centrifugation. At the end of step iv), the lithium salt is separated from the aqueous composition.

[0066] Step iv) can be implemented using one or more solid / liquid separation devices, such as filter presses or centrifuges.

[0067] Through steps i), ii), iii), and iv), residual solid lithium metal initially present in one or more monomers can be recovered in the form of salts. Furthermore, at the end of step iv), one or more lithium salts are separated from the aqueous composition, allowing the aqueous composition to be reused in new methods for extracting residual solid lithium metal, particularly in the new step i).

[0068] Step v): Washing lithium salt

[0069] The method may further include step v) for washing one or more lithium salts obtained in step iv). Rinsing or washing can be performed with water. Washing is preferably performed over an aqueous composition, particularly over a soaking tank or container. Alternatively, washing step v) can be performed by injecting clean water during filtration, particularly in a filter press. In particular, step v) improves the purity of the obtained lithium salt.

[0070] Step vi): Drying lithium salt

[0071] The method may further include step vi) for drying one or more lithium salts obtained in step iv) or v). Drying may be carried out at a temperature of about 60°C to about 100°C. Step vi) may be carried out using one or more devices for drying lithium salts, such as an oven or a heated tunnel.

[0072] Steps a) and b) : Cut and grind the monomers before step i).

[0073] Prior to step i), the method may further include step a) for cutting the component containing one or more monomers, preferably cutting all monomers in the component. This reduces the lithium dissolution time in step i) and improves the subsequent step ii) for separating the solids from the aqueous composition. According to this embodiment, step i) is then performed with the component containing one or more monomers cut, or with one or more cut monomers. Step a) can be carried out using one or more cutting devices, such as a guillotine, laser cutter, or ultrasonic cutter. Cutting step a) is a dry cutting step.

[0074] Prior to step i), the method may further include step b) for grinding the component containing one or more monomers, preferably grinding all monomers in the component. This reduces the lithium dissolution time in step i) and improves the subsequent step ii) for separating the solids from the aqueous composition. According to this embodiment, step i) is then performed with the component containing one or more monomers that has been ground, or with one or more ground monomers. Step b) can be carried out using one or more grinding devices, such as jaw mills or disc mills. The grinding devices may be equipped with cooling systems to prevent the material from heating up during grinding, thereby reducing industrial risks. Grinding step b) is a dry grinding step.

[0075] Step b) is preferably performed after step a). According to this embodiment, step i) is then performed using a component of one or more monomers that have been cut and ground, or using one or more monomers that have been cut and ground.

[0076] Step c): Oxidize the residual lithium from the monomer prior to step i).

[0077] Prior to step i), the method may further include step c) oxidizing the residual lithium to lithium oxide (Li₂O). This avoids generating too much hydrogen gas in step i). In particular, step c) reduces the reactivity of lithium prior to step i), thereby reducing industrial risks.

[0078] Step c) can be performed by heating one or more individual components, preferably to a temperature of about 300°C to about 400°C. Step c) can be performed using one or more heating devices, such as an oven, furnace, or heating tunnel.

[0079] Step c) can take approximately 30 minutes to approximately 2 hours.

[0080] Step c) can be performed without prior steps a) and / or b), or simultaneously with steps a) and / or b). Preferably, step c) is performed after grinding step b), particularly to accelerate the lithium metal oxidation kinetics.

[0081] The method, particularly steps i), i'), ii), ii'), iii), and iv), can be repeated with components of one or more other monomers, preferably with the aqueous composition from step iv) of a previous method. This means it can be recycled. The method is preferably carried out at atmospheric pressure and in ambient air. In other words, an inert atmosphere is not required.

[0082] Step d): Purify the aqueous composition

[0083] The method may further include step d), in which the aqueous composition containing dissolved lithium is purified. In this way, all compounds soluble in the aqueous composition from step ii) or step ii') are removed, except for lithium. These soluble compounds include solid electrolytes or quasi-solid electrolytes or derivatives thereof. In particular, at the end of step ii) or step ii'), the solid electrolyte or quasi-solid electrolyte is at least partially dissolved in the aqueous composition. The result is an aqueous composition containing one of the solid electrolytes or derivatives thereof and residual lithium.

[0084] Step d) is preferably performed by solid / liquid separation. Particularly preferred is step d) by hot filtration or hot centrifugation, and even more particularly preferred is it performed at a temperature of about 70°C to about 90°C. In step d), the solid electrolyte or quasi-solid electrolyte becomes insoluble in the aqueous composition upon heating and can be readily separated from lithium, which remains soluble in the aqueous composition, by filtration. Step d) can be implemented using one or more solid / liquid separation devices, such as a filter press or a centrifuge.

[0085] Step d) avoids excessive consumption of the acid or one of its precursors in step iii) and also improves the purity of the salt obtained in step iv).

[0086] The method may further include step i'), which involves adding at least one defoamer to the aqueous composition after step i) and before step ii). In practice, soaking step i) can lead to the formation of thick foam, which in turn can cause liquid overflow and necessitates stopping step i). The use of a defoamer prevents this. Different types of defoamers can be used, such as alcohol- and fatty acid-based defoamers, like the one sold under reference number "RM 761" (manufactured by Karcher), or polydimethylsiloxane-based defoamers, like the one sold under reference numbers "CQ-232", "CQ-233", and "CQ-234" (manufactured by NANHUI NEWMATERIAL CO., LTD).

[0087] A second object of the present invention is to provide a method for completely extracting lithium from a component comprising one or more energy storage cells containing solid lithium metal, the method comprising:

[0088] A) A first method for extracting lithium from an assembly of one or more energy storage cells, each cell comprising a negative electrode containing solid lithium metal, a positive electrode, a solid electrolyte or quasi-solid electrolyte, and optionally a current collector.

[0089] The component comprising one or more monomers includes a first edge and a second edge opposite to the first edge, wherein one or more negative electrodes of the one or more monomers protrude from the first edge, and one or more positive electrodes protrude from the second edge.

[0090] The method includes an extraction phase, which includes the following steps:

[0091] - Position the component so that one of the first edge and the second edge is below the other of the first edge and the second edge, and

[0092] - The component is heated to a temperature greater than or equal to the melting temperature of the solid lithium metal, referred to as the processing temperature.

[0093] The first extraction method yields a component containing one or more individual energy storage cells, and

[0094] B) A second method for extracting residual lithium according to the first objective of the present invention.

[0095] According to the first method of A)

[0096] When the component comprises multiple cells (i.e., at least two cells), each cell includes a positive electrode, a negative electrode containing solid lithium metal, a solid electrolyte or quasi-solid electrolyte, and optionally a current collector. The component includes a first edge and a second edge opposite to the first edge, the negative electrode of the cell protruding from the first edge, and the positive electrode protruding from the second edge. In this embodiment, the first method preferably further includes a step of cutting the electrical connection between the positive electrodes of at least two, and particularly all, cells of the component.

[0097] Each energy storage cell preferably includes:

[0098] - Negative electrodes containing solid lithium metal, especially those in layered form.

[0099] - Positive electrode, especially a layered positive electrode,

[0100] - A solid electrolyte or quasi-solid electrolyte containing lithium salts, particularly a layered solid electrolyte or quasi-solid electrolyte disposed between a positive electrode and a negative electrode, and

[0101] - Current collectors that are associated with the positive electrode and / or located on the side of the positive electrode.

[0102] In the first method according to A), "solid lithium metal" may comprise: pure lithium metal; or at least one lithium metal alloy; or a combination of pure lithium metal and at least one lithium metal alloy.

[0103] The components used may include a single or unique energy storage unit or multiple energy storage units, preferably assembled along an assembly direction, or particularly stacked. The assembly direction may be perpendicular to the plane formed by each energy storage unit.

[0104] According to a preferred embodiment of the invention, the component corresponds to a storage battery, and particularly preferably a storage battery in which individual cells are connected in series.

[0105] The component used in the method according to A) comprises solid lithium metal. According to a preferred embodiment of the invention, in the component of one or more monomers used in the method according to A), the solid lithium metal accounts for at least 80% by mass, preferably at least 85% by mass, and particularly preferably at least about 90% by mass relative to the total mass of solid lithium metal present in the component of one or more non-delithiation monomers.

[0106] The first method according to A) removes the majority of solid lithium metal from one or more monomeric components, leaving only residual solid lithium metal. The second method according to B) achieves the first objective of the invention and allows for the extraction of all residual solid lithium metal.

[0107] When “solid lithium metal” comprises a combination of different forms of lithium with different melting temperatures, such as those indicated above, then the heating step of one or more monomeric components is carried out at a processing temperature greater than or equal to the following temperatures:

[0108] - The lowest temperature among the different melting temperatures; and

[0109] - Preferably, the highest of the different melting temperatures.

[0110] Therefore, the first method according to A) proposes to recover solid lithium metal from the component by heating the component to a processing temperature greater than or equal to the melting temperature of solid lithium metal. Once the lithium metal melts, it is discharged naturally, in whole or in part, from each individual. Thus, the first method according to A) allows for the simple and uncomplicated recovery of the vast majority of solid lithium metal.

[0111] Furthermore, according to the first method in A), a specific orientation is proposed for each monomer, which is at least inclined. This orientation of each monomer facilitates the outflow of molten lithium from the monomer under the influence of gravity.

[0112] Furthermore, and most importantly, the first method according to A) preferably provides cutting the connection between the positive electrodes of at least two, more preferably all, of the monomers in the component. In other words, the cutting step allows the electrical connection between the positive electrodes of the component to be broken. Therefore, after the cutting step, the component comprises multiple monomers that are no longer electrically connected to each other, which reduces the reactivity of the component and thus reduces the risk of the component catching fire during lithium recovery.

[0113] The characteristic of the first edge is that it defines the side from which lithium must flow out once it is in a liquid state.

[0114] The first method according to A) can be implemented to process one or more individual components, particularly multiple individual components that form a battery pack and are connected together in parallel within the battery pack.

[0115] At least two single-unit components can be aligned side-by-side without overlapping, for example, in a direction parallel to the first edge.

[0116] heating

[0117] According to a non-limiting embodiment, the processing temperature is greater than or equal to 180.5°C.

[0118] According to one implementation scheme, the processing temperature is less than or equal to the maximum temperature, for example, 300°C.

[0119] Heating can be done using a heating plate or a heating cabinet.

[0120] Cutting

[0121] The cutting process can be performed in the following ways:

[0122] - Cut the connection line between the positive terminals along the boundary located, particularly at the second edge, on one side of the electrical connection line; or

[0123] - Cut the monomer along the cutting line located, in particular, at the boundary of the second edge, on one side of the monomer.

[0124] The first alternative allows solid lithium metal to remain in the module or not be removed from the module when the electrical connection is cut, which makes it possible to increase the lithium recycling yield.

[0125] In this first alternative, the connecting wire must be cut close enough to the second edge that there is no longer any contact between the different positive electrodes after the cut.

[0126] In the second alternative, to reduce the amount of lithium lost, the cutting must be performed immediately adjacent to the second edge.

[0127] For example, the cutting can be performed at a distance of less than or equal to 2 mm from the second edge "d", or less than or equal to 1% of the cell size between the first and second edges of the battery.

[0128] The cutting process can be performed using a guillotining cutter.

[0129] In this case, the component is inserted into a gate of appropriate size and power.

[0130] The cutting step can be performed before or after the heating step begins. In the latter case, preferably, the cutting step can be performed before the solid lithium metal begins to melt.

[0131] The cutting step can be performed before, after, or during the positioning step.

[0132] Charge

[0133] According to a particularly advantageous feature, the first method according to A) may further include a step of electrically charging one or more individual components prior to the extraction stage, the extraction stage being applied to the charged components.

[0134] Lithium extraction yield can be increased by electrically charging one or more individual components and performing an extraction stage on the electrically charged individual. In effect, the electrical charging of the individual components allows lithium ions to be moved to the negative electrode, thereby increasing the amount of recoverable lithium.

[0135] Each unit can be charged individually, or it can be charged by electrically charging one or more units of the same component.

[0136] compression

[0137] According to a particularly advantageous implementation, the extraction stage may also include the step of compressing one or more individual components.

[0138] Therefore, molten lithium is forced out of each monomer, thereby increasing the amount of lithium recovered.

[0139] The compression step can be performed continuously throughout the extraction phase, or discretely once or more times during the extraction phase. In the first case, each monomer undergoes partial or complete compression throughout the entire duration of the extraction phase. In the second case, the extraction phase includes moments when the components of the one or more monomers are not compressed.

[0140] Advantageously, the compression step can be performed by applying compression to the surface of the assembly of one or more monomers by sweeping the assembly from the second edge toward the first edge. Thus, molten lithium is gradually brought to / guided toward one or more negative electrodes from their protruding first edges, thereby increasing the amount of recovered lithium and reducing the risk of lithium coming into contact with one or more positive electrodes.

[0141] For example, the compression step can be performed by passing the component of one or more individual units between two rollers, or by using compression rollers that press the component of one or more individual units against the bearing surface.

[0142] Compression can be applied in successive passes, each pass sweeping across the surface of one or more individual components from the second edge toward the first edge.

[0143] The gap between the compression rollers, or the gap between the compression roller and the bearing surface, can correspond to the thickness of the one or more individual components minus the thickness of the solid lithium metal layer. This allows compression to be applied as long as solid lithium remains in the one or more individual components.

[0144] The gap between the two compression rollers, and the gap between the compression rollers and the bearing surface, can be reduced with each successive stroke, so that compression is always applied to the one or more individual components.

[0145] The speed at which the battery passes between the compression rollers, the speed of the compression rollers, and more generally the sweeping speed, can range from a few millimeters to tens of millimeters per second.

[0146] Removal of connectors and overflow

[0147] Additionally, the first method according to A) may include a step of removing at least one electrical connector, also known as a “crimp,” from the assembly of one or more individual units prior to the extraction stage. This facilitates the processing of the assembly of one or more individual units.

[0148] Additionally, the first method according to A) may include a step prior to the extraction stage of removing at least one of the components of the one or more monomers, particularly any material hanging over each edge.

[0149] position

[0150] According to the first version, the positioning step can position the one or more individual components in an orientation in which the first edge of the one or more individual components is located below the second edge of the one or more individual components.

[0151] Therefore, this orientation of the assembly of one or more individual units, and of each individual unit of the assembly of one or more individual units, facilitates the outflow of molten lithium from the individual unit under gravity, and avoids contact between molten lithium and the positive electrode or the current collector of the positive electrode, which could lead to an electrical short circuit or an electric arc, and such a short circuit could lead to a fire.

[0152] According to the preferred embodiment of this first version, the positioning step can vertically orient the component of one or more individual units, with the first edge face downwards.

[0153] Therefore, the situation where molten lithium flows out of each monomer under the influence of gravity is improved.

[0154] In addition, the risk of molten lithium coming into contact with one or more positive electrodes is reduced or even eliminated.

[0155] In this first version, preferably, the step of heating the component of one or more monomers can be carried out under an inert gas atmosphere. Therefore, the method according to the invention reduces the risk of accidents, particularly the risk of fire. Additionally, it avoids the formation of contaminants that may arise during lithium extraction due to undesirable or even uncontrolled physicochemical reactions.

[0156] According to a non-limiting embodiment, the inert gas may be any one of the following gases or include any one of the following gases: helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and radon (Rn).

[0157] According to another embodiment of this first version, the step of heating the component of one or more individual units can be performed under a vacuum.

[0158] According to another embodiment of the first version, the step of heating one or more individual components can be carried out in dry air, specifically dry air containing less than 0.002% H2O by mass.

[0159] According to the second version, the positioning step can position the one or more individual components in an orientation where the first edge of the one or more individual components is located above the second edge of the one or more individual components. In this case, the extraction stage also includes a step of immersing the one or more individual components in a liquid called a processing liquid, which is denser than liquid lithium and electrically insulating, prior to the heating step.

[0160] The second version proposes a specific orientation for each cell, which is at least tilted, such that one or more negative electrodes protruding from their first edges are positioned above the horizontal plane of one or more positive electrodes protruding from their second edges, opposite the first edges. This orientation of each cell facilitates the outflow of molten lithium from the cell by density difference, while preventing contact between the molten lithium and the positive electrode or its current collector, which could lead to an electrical short circuit and potentially a fire. Furthermore, immersing the assembly of one or more cells in a liquid improves the dissipation of heat energy from the cells, particularly during short circuits, thus significantly limiting their impact.

[0161] In this application, "density" refers to the ratio between the density of the liquid under consideration and the density of water.

[0162] According to the preferred embodiment of this second version, the positioning step can vertically orient the component of one or more individual units, with the second edge face downwards.

[0163] Therefore, the situation where molten lithium flows out of each monomer due to density difference is improved.

[0164] In addition, the risk of contact between molten lithium and the positive electrode is reduced or even eliminated.

[0165] Preferably, the soaking step can be performed by completely immersing one or more individual components in the processing liquid.

[0166] The liquid can be a natural or synthetic oil, and it includes the following physicochemical properties:

[0167] - Hydrophobic and non-reactive with lithium

[0168] - Electrical insulation,

[0169] - Density greater than that of lithium,

[0170] - It is thermally stable above the melting temperature of lithium, which is 180.5°C.

[0171] - The flash point and auto-ignition point should be as high as possible.

[0172] A third object of the present invention is to provide an apparatus for extracting residual lithium from a component comprising one or more energy storage cells containing residual solid lithium metal, characterized in that it comprises:

[0173] - A tank for immersing components of one or more monomers in an aqueous composition;

[0174] - One or more devices for separating solids (and / or solid residues) from an aqueous composition;

[0175] - Apparatus for adding an acid or one of its precursors to an aqueous composition; and

[0176] - One or more solid / liquid separation devices for the recovery of one or more lithium salts.

[0177] The extraction device according to the third purpose allows for the implementation of the method according to the first purpose of the invention.

[0178] The device for adding one of the acids or their precursors to an aqueous composition can be a diaphragm metering pump. This allows for the introduction of a precise volume of acid solution or its precursor, previously prepared in a tank, based on the concentration of lithium present in the aqueous composition.

[0179] Solid / liquid separation equipment for recovering lithium salts can be as defined in the first objective of this invention.

[0180] The residual lithium extraction apparatus may also include equipment for heating and / or stirring the aqueous composition as defined in the first objective of the invention.

[0181] The residual lithium extraction apparatus may also include equipment for washing lithium salts and / or for washing components of one or more monomers, in order to implement the washing steps of the method described above according to the first objective of the invention.

[0182] The residual lithium extraction apparatus may also include one or more devices for recovering the aqueous composition for re-injection into the soaking tank (in order to implement the novel method according to the first objective of the invention). This allows the aqueous composition to be recycled in a closed loop.

[0183] Typically, a residual lithium extraction apparatus may include any combination of devices configured to implement at least one feature described in the first objective of the invention, which will not be repeated in detail here for the sake of brevity.

[0184] A fourth object of the present invention is to provide an integrated facility for extracting lithium from one or more energy storage cells, each cell comprising a positive electrode, a negative electrode containing solid lithium metal, a solid electrolyte or quasi-solid electrolyte, and optionally a current collector.

[0185] The component includes a first edge and a second edge opposite to the first edge, wherein one or more negative electrodes of one or more monomers protrude from the first edge, and one or more positive electrodes protrude from the second edge.

[0186] The extraction facility includes:

[0187] * A lithium extraction device that produces one or more monomers containing residual solid metallic lithium.

[0188] The lithium extraction device includes:

[0189] - A device for positioning the component in an orientation in which one of the first edge and the second edge is located below the other of the first edge and the second edge; and

[0190] - A heating device configured to heat the component to a temperature greater than or equal to the melting temperature of the solid lithium metal, said temperature being referred to as the processing temperature.

[0191] * A residual lithium extraction apparatus according to a third objective of the present invention.

[0192] The lithium extraction apparatus may also include a device for cutting the electrical connection between at least two, particularly all, the positive electrodes of the components.

[0193] Typically, the facility may include devices configured to implement any combination of at least one feature described in the second objective of the invention, which will not be repeated in detail here for the sake of brevity.

[0194] For example, cutting equipment may include a gate.

[0195] In particular, the heating equipment may include an oven (heating chamber) or a heating plate.

[0196] Advantageously, the oven can be filled with inert gas, dry air, or evacuated, or even filled with a processing liquid with a density greater than that of liquid lithium.

[0197] The lithium extraction apparatus may also include equipment for compressing the components.

[0198] The compression device may include at least one roller.

[0199] Specifically, the compression device may include a single roller that presses the one or more individual components against a bearing surface. The bearing surface may be heated to accelerate the temperature rise of the one or more individual components.

[0200] Alternatively, the compression device may include two rollers, with one or more individual components passing between the two rollers.

[0201] Typically, compression equipment can be configured to apply continuous compression throughout the extraction phase.

[0202] Alternatively, the compression device can be configured to apply compression at one or more separate points during the extraction phase. In this case, the extraction phase includes the time when the one or more individual components are not compressed.

[0203] Advantageously, the compression device can be configured to apply a constant or variable value of compression by gradually moving from the second edge to the first edge or by sweeping across the surface of the component of one or more monomers. Thus, molten lithium is gradually brought to / guided toward the first edge located at a lower position, which increases the amount of recovered lithium and reduces the risk of contact between lithium and the positive electrode.

[0204] When using one or two compression rollers, compression can be applied to the assembly in successive passes. Each pass applies compression by sweeping across the surface of the assembly from the second edge to the first edge. At the end of each pass, compression can be stopped by a separation roller or by passing the separation roller against the bearing surface, returning to the second edge to restart a new pass.

[0205] The gap between rollers, or the gap between the compression roller and the bearing surface, can be reduced with each pass, especially between two consecutive passes.

[0206] Compression can be applied to at least two components of one or more units using the same compression device, namely a set of rollers or rollers that interact with the bearing surface.

[0207] Description of Drawings and Embodiments

[0208] Further benefits and features will become apparent upon examination of the detailed description of the fully non-limiting embodiments, along with the accompanying drawings, in which:

[0209] - Figure 1 This is a schematic diagram of a first example embodiment of the method according to the first objective of the present invention;

[0210] - Figure 2 This is a schematic diagram illustrating a second example embodiment of the method according to the first objective of the present invention;

[0211] - Figure 3 This is a schematic diagram illustrating an example embodiment of the method according to the second objective of the present invention.

[0212] It should be clearly understood that the embodiments described below are by no means limiting. In particular, variations of the invention are conceivable that include only selections of the features disclosed below, separate from the other disclosed features, if such selection is sufficient to provide a technical benefit or to distinguish the invention from the prior art. Such selections include at least one preferred functional feature that lacks structural detail, or has only a portion of structural detail, if such portion is sufficient to provide a technical benefit or to distinguish the invention from the prior art.

[0213] In the accompanying drawings, the same reference numerals are used for features common to multiple drawings.

[0214] Figure 1 The method illustrating the first objective of the invention includes a first step i): immersing one or more monomeric components in an aqueous composition, preferably in water, each monomer comprising residual solid lithium metal, a positive electrode, a current collector associated with the positive electrode, and a solid electrolyte or quasi-solid electrolyte. Step i) dissolves the residual solid lithium metal in the aqueous composition. The method may further include a step i') of adding at least one defoamer to the aqueous composition. Step i') is as defined in this invention. Once dissolution is complete, a solid / liquid separation step ii) is performed to separate the solids and solid residues from the aqueous composition. For example, the solids and solid residues are removed or discharged from the aqueous composition. Step ii) may further include a step ii') of washing or rinsing the solids (or solid residues), preferably with water. Washing is preferably performed above the aqueous composition, particularly above an immersion tank. This improves the recovery yield of lithium salts by the method. Once the solids and solid residues have been removed from the aqueous composition, in step iii), an acid, such as phosphoric acid or a CO2 stream (a carbonic acid precursor), is added to the aqueous composition to form one or more lithium salts insoluble in the aqueous composition. The next step iv) involves recovering the formed lithium salts by solid / liquid separation, preferably by filtration.

[0215] Figure 2 The method of the first objective of the present invention shown includes the above-described method for... Figure 1 The described steps i), i'), ii), ii'), iii), and iv) are included, and step i) is preceded by any one of steps a), b), and c), or a combination of at least two of steps a), b), and c). These steps are optional. Figure 2The assembly, comprising one or more monomers, is cut according to step a) to obtain sheets or blocks of one or more monomers, each monomer comprising residual solid lithium metal, a positive electrode, a current collector associated with the positive electrode, and a solid or quasi-solid electrolyte, thereby improving the solubility of lithium in the aqueous composition as in step i). Step a) may be followed by step b), wherein the cut assembly is ground to obtain a ground assembly of one or more monomers, further improving the solubility of lithium in the aqueous composition as in step i). Step b) may be followed by step c): heating the assembly to oxidize the residual lithium. Step c) avoids generating too much hydrogen gas during step i). The method may also include step i') of adding at least one defoamer to the aqueous composition. Step i') is optional and as defined in this invention.

[0216] Then Figure 2 The methods shown include, for example, those for Figure 1 The described step i), then optionally step i'), followed by as for Figure 1 The solid / liquid separation step ii) and washing step ii' described.

[0217] The aqueous composition obtained from steps ii) and ii') can be purified in step d) to remove all compounds soluble in the aqueous composition except lithium. This step d) is preferably carried out by solid / liquid separation, and more particularly by hot filtration. In step d), the solid electrolyte or quasi-solid electrolyte and / or its derivatives become insoluble in the aqueous composition upon heating and can be readily separated from lithium, which is still soluble in the aqueous composition, by filtration.

[0218] Then Figure 2 The methods shown include, for example, those for Figure 1 Steps iii) and iv) are described, optionally followed by step v) washing the lithium salts. These lithium salts may optionally be dried in step vi).

[0219] Figure 3 The method of the second objective of the present invention shown includes, prior to the method of the first objective according to the present invention (method according to B), as... Figure 1 and Figure 2 As shown, a method for extracting the majority of solid lithium metal from a component of one or more cells (according to method A), each cell comprising a negative electrode containing solid lithium metal, a positive electrode, an optional current collector, and a solid electrolyte or quasi-solid electrolyte. Such a method according to method A includes an optional step during which the electrical connectors of the battery, particularly the current collector, also known as a "crimper", are removed.

[0220] In a subsequent optional step, any overhanging material, particularly solid lithium metal, is removed from each side edge of the component.

[0221] Then, the method according to B) of the second objective of the invention includes a stage of extracting metallic lithium from the monomer of the component. The extraction stage includes a step of positioning the component with the negative electrode protruding from its first edge below the positive electrode and / or the current collector protruding from its second edge. Specifically, this step orients the component in a vertical direction, i.e., parallel to the gravity vector, with the negative electrode facing downwards from its first protruding edge. Preferably, but without limitation, the component remains in this orientation throughout the extraction stage.

[0222] The extraction stage also includes heating the component to a temperature greater than or equal to the melting temperature of the solid lithium metal present in the component, such as a processing temperature of 180.5°C. This temperature will cause the solid lithium metal to melt and be extracted from each monomer by natural flow under gravity. Preferably, but by no means limited, the component is maintained at this temperature throughout the extraction stage. Advantageously, the heating step is carried out in a sealed chamber filled with inert gas.

[0223] The extraction stage may also include an optional step of compressing the assembly to expel molten lithium from each cell of the assembly. Compression may be performed continuously during all or part of the extraction stage. Optionally, the compression step may be repeated on several separate occasions during the extraction stage. Preferably, the compression step is performed gradually or by sweeping across the battery surface, starting from the positive electrode at its protruding second edge and moving towards the negative electrode at its protruding first edge.

[0224] The method includes the step of severing the electrical connections between the positive electrodes / current collectors of at least two, and particularly all, of the cells in the component. This severing step allows the electrical connections between the positive electrodes of the cells in the component to be broken, thereby reducing the reactivity of the component. Therefore, the risk of the component igniting during the extraction phase is reduced, enabling more reliable and lower-risk recovery of solid lithium metal.

[0225] In the example shown, the step of cutting the electrical connection is performed before the extraction stage. Alternatively, the cutting step may be performed during the extraction stage, before, during, or after the positioning step, or before, during, or after the heating step.

[0226] Furthermore, the present invention is not limited to the embodiments described above, but can be applied to solid electrolyte or quasi-solid electrolyte components or batteries that do not contain polymers at the cathode. The present invention can be applied to any battery having solid lithium metal and a cathode that is stable up to the melting temperature of solid lithium metal.

[0227] Example 1: Preparation of a storage battery containing residual solid lithium metal

[0228] Lithium metal polymer (LMP) has been disassembled. ®The battery module was then removed from the individual battery cells for this embodiment. Next, a lithium melt extraction step was performed according to the method described in WO2023 / 036741 A2. The obtained metallic lithium was weighed. In this embodiment, 91% of the metallic lithium initially present in the cell was extracted. The remaining solid metallic lithium remained in the battery cell.

[0229] Example 2: Extraction of residual lithium using the method according to the present invention

[0230] The all-solid-state lithium battery-type energy storage cell, prepared as in Example 1 and containing residual lithium (approximately 10% by mass relative to the total mass of lithium present in the initial battery), was immersed in an immersion tank containing water (as an aqueous composition) to cover the battery with water (approximately 18 L of water). After immersion in the aqueous composition (water) for approximately 12 hours, the dissolution of metallic lithium in the water was completed [step i).

[0231] Lithium concentration was measured by analyzing the bath water (soaking water or aqueous composition) using inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The results showed that all residual Li had been dissolved and recovered in the aqueous composition.

[0232] Step i) also results in the stratification of the electrolyte, positive electrode, and current collector membrane. Remove these solids from the tank [step ii)] and rinse over the tank with approximately 2 L of water [step ii')].

[0233] Then, under mechanical stirring, about 2.25 g of phosphoric acid (H3PO4 85%, Sigma Aldrich) was added to about 1 L of the aqueous composition prepared above, containing residual lithium and previously heated to 60°C [step iii). After reacting for 2 hours, the aqueous composition was filtered to separate the lithium salt from the aqueous composition [step iv]. The obtained lithium salt was then dried at 100°C for 3 hours [step vi]. This produced a white powder.

[0234] Example 3: Extraction of residual lithium using the method according to the present invention

[0235] Three all-solid-state lithium-ion battery cells containing residual lithium (approximately 10% by mass relative to the total mass of lithium present in the initial battery) were immersed in an immersion tank containing water (as an aqueous composition) to cover the batteries with water (approximately 37 L of water). After immersion in water for approximately 20 hours, the dissolution of metallic lithium in the water was completed [step i).

[0236] The lithium concentration in the aqueous composition was measured by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The results showed that all residual Li was dissolved and recovered in the aqueous composition. The results also indicated that the amount of lithium dissolved in the aqueous composition was proportional to the amount of monomers impregnated in the composition.

[0237] Step i) also results in the stratification of the electrolyte, positive electrode, and current collector membrane. Remove the solids from the tank [step ii)] and rinse over the tank with approximately 3 L of water [step ii')].

[0238] The resulting aqueous composition is heated to 95°C for 1 hour to render the electrolyte or its polymeric component insoluble. The resulting composition is filtered to produce a purified aqueous composition [step d].

[0239] Then, under mechanical stirring, about 9 g of phosphoric acid (H3PO4 85%, Sigma Aldrich) was added to about 1 L of the aqueous composition prepared above, which contained residual lithium and had previously been heated to 60°C [step iii). After reacting for 2 hours, the aqueous composition was filtered to separate the lithium salt from the aqueous composition [step iv]. The obtained lithium salt was then dried at 100°C for 3 hours [step vi]. This produced a white powder.

[0240] X-ray diffraction (XRD) analysis of the obtained white powder sample showed diffraction peaks corresponding to the Li3PO4 phase. No other crystalline phases were observed. This result indicates the formation of a product mainly composed of Li3PO4.

[0241] The pH of the remaining aqueous composition after step iv) is 7.6. Therefore, it can be reused as the aqueous composition used in step i) in the new method according to the invention.

[0242] The solid residue recovered from step ii') was ground and analyzed by X-ray diffraction (XRD). The analysis results showed that the solid consisted only of LiFePO4 used as the positive electrode active material and aluminum used as the current collector. This result confirms that the solid separated from the aqueous composition at the end of step ii') did not contain metallic lithium or its derivatives, such as lithium hydroxide or LiOH.

[0243] Example 4: Extraction of residual lithium using the method according to the present invention

[0244] Example 2 was repeated in an aqueous composition using a CO2 stream instead of phosphoric acid. The CO2 stream through the aqueous composition resulted in the precipitation of H2CO3 carbonate and Li2CO3 salt. The recovery yield of Li2CO3 was improved by heating the solution prior to CO2 injection, due to the low solubility of Li2CO3 in hot water.

[0245] Maintain the CO2 flow until an aqueous composition with a pH of 7 is obtained.

[0246] Example 5: Extraction of residual lithium using the method according to the present invention

[0247] Example 2 is repeated by performing the cutting step [step a)] before step i).

[0248] For this purpose, the monomer was longitudinally cut into 5 strips. The 5 strips were then placed in a tank containing approximately 18 L of water (as an aqueous composition) [step i). After only 2 hours, the dissolution of the metallic lithium was complete and the film was completely delaminated. The other steps were the same as described in Example 2.

[0249] Cleavage reduces the dissolution time of residual Li.

[0250] Of course, the number of bands is just an example, as the improvement in dissolution time is unrelated to the number of bands. One or more monomers can also be cut into other shapes (e.g., blocks).

[0251] Example 6: Separation of active material and current collector

[0252] Using the solid containing LiFePO4 and aluminum obtained in Example 3: Approximately 700 g of the solid was pre-ground using a Shini SG-1628N (2.2 kW) knife mill equipped with a 160 × 280 mm cutting chamber having two fixed blades and 3 × 4 staggered moving blades. A sizing grid was used, resulting in a final particle size of 5 mm to 10 mm. The resulting powder was then passed through an ECS-40 eddy current separator. Two fractions were obtained, one rich in aluminum and the other primarily containing the active material, also known as black lumps. The method according to the invention allows for the complete recovery of lithium, the active material, the current collector metal, and the aqueous composition used in step i).

Claims

1. A method for extracting residual lithium from a component containing one or more energy storage cells, the method comprising at least the following steps: i) Immerse the component in an aqueous composition. ii) Separating solids from the aqueous composition, said solids being positive electrode active materials and / or current collectors. iii) Adding at least one acid or its precursor, said acid or its precursor being capable of forming at least one lithium salt insoluble in the aqueous composition, and iv) Recover lithium salts.

2. The method according to claim 1, characterized in that, The aqueous composition contains at least 90% by weight of water relative to the total weight of the aqueous composition.

3. The method according to claim 1 or 2, characterized in that, The acid or one of its precursors is selected from inorganic acids, carboxylic acids, and mixtures thereof.

4. The method according to any one of the preceding claims, characterized in that, The acid or one of its precursors is added to the aqueous composition at a rate of at least 10 g / L of the aqueous composition.

5. The method according to any one of the preceding claims, characterized in that, The aqueous composition at the end of step iii) has a neutral pH.

6. The method according to any one of the preceding claims, characterized in that, Step ii) includes or is followed by step ii' of washing the solids.

7. The method according to any one of the preceding claims, characterized in that, Prior to step i), it also includes step a) for cutting the component of one or more individual units.

8. The method according to any one of the preceding claims, characterized in that, Prior to step i), it also includes step b) for grinding the components of the one or more monomers.

9. The method according to any one of the preceding claims, characterized in that, Prior to step i), it also includes step c) for oxidizing the residual lithium to lithium oxide.

10. The method according to any one of the preceding claims, characterized in that, It also includes step d), during which the aqueous composition containing dissolved lithium is purified.

11. A method for completely extracting lithium from a component comprising one or more energy storage cells containing solid lithium metal, the method comprising: A) A first method for extracting lithium from an assembly of one or more energy storage cells, each cell comprising a negative electrode containing solid lithium metal, a positive electrode, a solid electrolyte or quasi-solid electrolyte, and optionally a current collector. The component comprising one or more monomers includes a first edge and a second edge opposite to the first edge, wherein one or more negative electrodes of the one or more monomers protrude from the first edge, and one or more positive electrodes protrude from the second edge. The method includes an extraction phase, which includes the following steps: - Position the component so that one of the first edge and the second edge is below the other of the first edge and the second edge, and - The component is heated to a temperature greater than or equal to the melting temperature of the solid lithium metal, referred to as the processing temperature. The first extraction method yields a component containing one or more individual energy storage cells, and B) A second method for extracting residual lithium as defined in any of the preceding claims.

12. The method according to claim 11, characterized in that, It also includes the step of cutting the electrical connection between at least two, and in particular all, the positive electrodes of the component.

13. An apparatus for extracting residual lithium from a component comprising one or more energy storage cells containing residual solid lithium metal. Its features are, It includes: - A tank for immersing components of one or more monomers in an aqueous composition; - One or more devices for separating solids from an aqueous composition; - Apparatus for adding an acid or one of its precursors to an aqueous composition; and - One or more solid / liquid separation devices for the recovery of one or more lithium salts.

14. An integrated facility for extracting lithium from one or more energy storage cells, each cell comprising a positive electrode, a negative electrode containing solid lithium metal, a solid electrolyte or quasi-solid electrolyte, and optionally a current collector. The component includes a first edge and a second edge opposite to the first edge, wherein one or more negative electrodes of the one or more monomers protrude from the first edge, and one or more positive electrodes protrude from the second edge. The extraction facility includes: * A lithium extraction device that produces one or more monomers containing residual solid metallic lithium. The lithium extraction device includes: - A device for positioning the component in an orientation in which one of the first edge and the second edge is located below the other of the first edge and the second edge; and - A heating device configured to heat the component to a temperature greater than or equal to the melting temperature of the solid lithium metal, said temperature being referred to as the processing temperature. * The residual lithium extraction apparatus as defined in claim 13.

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