Process for extracting lithium from an electric battery containing lithium with improved energy balance

Abstract

The invention relates to a method (300) for extracting lithium from an electric battery, comprising an extraction phase (302), carried out, at least in part, in one or more chambers and comprising the steps of: heating (304) said battery to a processing temperature greater than or equal to the melting temperature of metallic lithium; compressing (306) said battery to remove the molten lithium from the battery; said extraction phase (302) further comprising circulating a flow in said chamber, or in at least one of said chambers; said method (300) further comprising recovering (320) at least a portion of the energy from the flow exiting said chamber. It also relates to a system implementing such a method. Figure: Fig. 3

Description

Title of the invention: Process for extracting lithium from an electric battery comprising lithium with improved energy balance

[0001] The present invention relates to a method for extracting lithium from an electric battery comprising lithium, in particular metallic lithium, with an improved energy balance. It further relates to a system implementing such a method.

[0002] The field of the invention is the field of recycling lithium found in electric batteries comprising lithium, in particular metallic lithium, and in particular metallic lithium-based batteries, and even more particularly Lithium-Metal-Polymer batteries. State of the art

[0003] Lithium-based batteries, particularly metallic lithium batteries, are known, such as Lithium-Metal-Polymer (LMP) batteries (LMP®), which comprise a metallic lithium anode, a cathode consisting of a polymer-based layer and active material, an aluminum current collector, and, between the anode and cathode, an electrolyte comprising a mixture of polymer and lithium salts. These batteries are increasingly used, for example, in electric vehicles or in power stations. Thus, the number of lithium-based batteries has been steadily increasing for several years, and the example of LMP batteries, given purely as an illustration, is by no means limiting.

[0004] The lifespan of lithium-containing batteries is not infinite. Even at the end of its life, such a battery still contains valuable lithium that can be reused and whose value is significant, not to mention the regulatory obligation to recover said lithium.

[0005] For example, a process for recovering metallic lithium from a battery is known, described in the international application published under number WO2020 / 161339 AL. This process is very efficient and allows for the safe recovery of almost all the lithium present in a battery cell by heating, to a temperature greater than or equal to the melting temperature of metallic lithium, and then compression.

[0006] However, the inventors noted that heating is energy-intensive. Indeed, to melt the metallic lithium in the battery, the battery must be heated to a processing temperature of 185°C or higher, which is energy-intensive.

[0007] One object of the present invention is to remedy this drawback.

[0008] Another object of the invention is to propose a method for recovering lithium from a battery with an improved energy balance. Description of the invention

[0009] The invention makes it possible to achieve at least one of these objectives by a process for extracting lithium from an electric battery comprising metallic lithium, said process comprising a lithium extraction phase, carried out, at least in part, in one or more chambers, said extraction phase comprising the following steps: - heating said battery to a temperature, called the processing temperature, greater than or equal to the melting point of metallic lithium; - compression of said battery to evacuate the molten lithium out of the battery; said extraction phase further comprising a circulation of a flow in said enclosure, or in at least one of said enclosures; said process further comprising recovery of at least part of the energy of the outgoing flow from said enclosure, or from at least one of said enclosures.

[0010] In current processes, the energy used to heat the battery is simply rejected, or lost, in the form of waste heat.

[0011] Unlike current solutions, the invention proposes circulating a flow within the enclosure, or at least one of the enclosures, used during the lithium extraction phase. This flow contains waste energy, in the form of waste heat or volatile organic compounds (VOCs), as will be described later. The invention proposes recovering at least some of this waste energy, thereby improving the overall energy balance of the extraction of metallic lithium from an electric battery. The waste energy recovered from the outgoing flow can be reused within the framework of the present invention, thereby reducing the overall energy consumption of the solution proposed by the present invention, and / or in another industrial installation, thereby reducing the overall energy impact and carbon footprint of the lithium extraction according to the invention.

[0012] The battery may comprise a single cell, or several cells.

[0013] Generally, the battery may include a first border from which the negative electrodes of the cells protrude and a second border, opposite to said first border, from which the positive electrodes of the cells protrude.

[0014] The processing temperature is greater than or equal to the melting point of lithium, and in particular of metallic lithium.

[0015] In particular, the processing temperature is greater than or equal to 185°C.

[0016] According to one embodiment, the treatment temperature may be less than or equal to a maximum temperature, for example 300 °C.

[0017] According to embodiments, the lithium extraction phase may include the circulation of a flow, referred to as the first evacuation flow, denoted FE1 hereafter, during the heating step, in particular to evacuate at least part of the VOCs released by the battery during said heating step.

[0018] Indeed, the inventors of the present invention observed that heating a lithium battery is accompanied by the emission of a significant amount of VOCs. These VOCs can cause a fire, particularly at the battery processing temperature, which makes the industrialization of the lithium extraction process difficult. To overcome this drawback, the invention proposes circulating a first exhaust flow FE1 during the heating stage, when the battery is heated by a means other than a heating flow.

[0019] In the case where the invention uses a first evacuation flow FE1 during the heating step, the battery can be heated by any means of heating by dissipation, conduction, or radiation. For example, the battery can be heated using one or more heating plates arranged in contact with, or near, the battery.

[0020] The first evacuation flow FE1 can be a gaseous flow.

[0021] The first exhaust flow FE1 can be an air flow, in particular dry air.

[0022] The first exhaust flow FE1 can be a neutral gas flow, such as argon (Ar).

[0023] The first exhaust flow FE1 can be at ambient temperature.

[0024] Preferably, the first evacuation flow FE1 can be at a temperature higher than the ambient temperature so as not to cool the battery.

[0025] According to embodiments, the temperature of the first evacuation flow FE1 can be variable and in particular adjustable.

[0026] According to a non-limiting example of embodiment, the first evacuation flow FE1 can be at a temperature of around 60°C or 65°C.

[0027] According to embodiments, the extraction phase may include a circulation, during the heating step, of a flow, called heating flow, and noted FC in the following, to heat the battery.

[0028] In this case, the heating of the battery is done partially or totally by the heating flow FC.

[0029] In this case, it is not necessary to use the first evacuation flow FE1 mentioned above.

[0030] The heating flow FC can be a gaseous flow.

[0031] The FC heating flow can be an air flow, in particular dry air.

[0032] The heating flux FC can be a neutral gas flux, such as argon (Ar).

[0033] The heating flux FC can be at a temperature greater than or equal to the processing temperature. For example, the FC heating flux can be at a temperature of 185°C.

[0034] According to embodiments, the temperature of the heating flow FC can be variable and in particular adjustable.

[0035] According to embodiments, the extraction phase may include the circulation of a flow, called the second evacuation flow, hereafter referred to as FE2, during the compression step, in particular to evacuate at least part of the VOCs released by the battery during said compression step.

[0036] Thus, the VOCs released by the battery during the compression stage are vented outside the enclosure. The inventors observed that the battery releases a significant amount of VOCs during the compression stage. More specifically, during the compression stage, the battery releases a greater quantity of VOCs than during the heating stage. Venting the VOCs outside the enclosure during the compression stage further enhances the safety of lithium extraction from a lithium battery.

[0037] The second exhaust flow FE2 can be used regardless of the embodiment for heating the battery, i.e. heating by use or not of a heating flow FC.

[0038] When a first evacuation flow FE1 is used, then the second evacuation flow FE2 can be, partially or totally, composed of said first evacuation flow FE1.

[0039] When a heating flow FC is used, then the second exhaust flow FE2 can be, partially or totally, composed of said heating flow FC.

[0040] The second evacuation flow FE2 can be a gaseous flow.

[0041] The second exhaust flow FE2 can be an air flow, in particular dry air.

[0042] The second exhaust flow FE2 can be a neutral gas flow, such as argon (Ar).

[0043] The second exhaust flow FE2 can be at ambient temperature.

[0044] Preferably, the second exhaust flow FE2 can be at a temperature above ambient temperature so as not to cool the battery.

[0045] According to an example embodiment, the second evacuation flow FE2 can be at a temperature greater than or equal to the processing temperature so as not to cool the battery and stop the flow of lithium during compression.

[0046] According to embodiments, the temperature of the second evacuation flow FE2 can be variable and in particular adjustable.

[0047] According to the invention, part or all of the extraction phase is carried out in one or more enclosures.

[0048] According to embodiments, the heating step and the compression step can be carried out in the same common enclosure.

[0049] According to embodiments, the heating step can be carried out in an enclosure, called a heating enclosure.

[0050] Alternatively, or in addition, the compression step can be carried out in an enclosure, called a compression enclosure.

[0051] In particular, the heating stage and the compression stage can be carried out in separate enclosures.

[0052] The heating and compression chambers can be glued together. Alternatively, the heating and compression chambers can be spaced apart.

[0053] According to some embodiments, the heating chamber can be used to heat several batteries simultaneously. Indeed, the heating stage is longer than the compression stage, making it possible to heat several batteries at the same time.

[0054] According to embodiments, the process according to the invention may include a battery cooling step after the compression step.

[0055] This cooling step can be carried out in a dedicated enclosure, called a cooling enclosure, or in an enclosure common to the compression step, for example.

[0056] According to embodiments, the recovery step may include a recirculation of at least part of the outgoing flow into the enclosure or into at least one enclosure.

[0057] In this case, the outgoing flow is reinjected into the enclosure, or at least one of the enclosures, to be reused in the process according to the invention and thus exploit the thermal energy of said outgoing flow.

[0058] For example, the outgoing flow can be reused as a heating flow and / or as an exhaust flow.

[0059] In this case, the process according to the invention may include, before recirculation / reinjection of the outgoing stream, the removal of at least part, or all, of the VOCs found in said outgoing stream.

[0060] VOCs found in the outgoing stream can be eliminated using any known technique.

[0061] According to some embodiments, the VOCs present in the outgoing stream can be eliminated by trapping said VOCs, for example with a carbon filter or a carbon column. In this case, the outgoing stream is circulated through said filter, or of said column, with carbon which retains VOCs and therefore allows the elimination of said VOCs present in said outgoing stream.

[0062] According to embodiments, the recovery step may include combustion, or oxidation, of at least part of the VOCs found in the outgoing stream.

[0063] In particular, when the outgoing stream is used during the heating and / or compression stages, it may contain VOCs as explained above. These VOCs represent a valuable source of energy. Their combustion transforms these VOCs into thermal energy, which can then be used within the framework of the present invention or in an external installation.

[0064] According to embodiments, the recovery step may include storage of at least part of the heat from the outgoing stream, possibly after combustion of VOCs.

[0065] Heat storage can for example be achieved by transferring said heat to a heat transfer fluid, denoted FCA hereafter, stored in a reservoir.

[0066] The heat transfer fluid (HFF) can be water, oil, or any other heat transfer fluid that can be stored in a tank. For example, the heat transfer fluid could be Therminol®.

[0067] According to some embodiments, the valorization step may include heating an incoming flow into an enclosure, by heat transfer between the outgoing flow and said incoming flow.

[0068] In this case, at least part of the heat from the outgoing flow is transferred to the incoming flow to heat it before the latter is introduced into the enclosure.

[0069] According to embodiments, the incoming flow and the outgoing flow may concern the same enclosure.

[0070] In other words, in this case, at least part of the energy of the outgoing flow from an enclosure is used to heat an incoming flow into said enclosure.

[0071] For example, at least a portion of the energy of the outgoing flux: - the common enclosure can be used to heat a flow entering said common enclosure; or - of the heating chamber, respectively of the compression chamber, can be used to heat a flow entering said heating chamber, respectively into said compression chamber.

[0072] According to embodiments, the incoming flow and the outgoing flow may concern different enclosures.

[0073] In other words, in this case, at least part of the energy of the outgoing flow from one enclosure is used to heat an incoming flow into another enclosure.

[0074] For example, at least a portion of the energy of the outgoing flux: - the heating chamber can be reused to heat an incoming flow into the compression chamber; and / or - the compression chamber can be reused to heat an incoming flow into the heating chamber; and / or - of the cooling chamber can be reused to heat an incoming flow into the heating chamber and / or to heat an incoming flow into the compression chamber.

[0075] According to embodiments, the recovery step may include heating another stream which is used in another application, or in another installation, with at least part of the energy from the outgoing stream.

[0076] For example, such a flow may be a flow used for the generation of electricity.

[0077] According to embodiments, the heat exchange between the outgoing flow and another flow can be carried out in a heat exchanger receiving said flows.

[0078] According to embodiments, the heat exchange between the outgoing flow and another flow can be achieved via a heat pump circuit.

[0079] According to embodiments, the process according to the invention may further include a measurement of the concentration of at least one volatile organic compound in the enclosure, or in at least one enclosure, during the extraction phase.

[0080] The measurement can be carried out during the heating stage.

[0081] Alternatively, or in addition, the measurement can be carried out during the step of compression.

[0082] The measurement can be carried out in the common area, if necessary.

[0083] The measurement can be carried out in the heating chamber, and / or in the chamber of compression, and / or in the cooling chamber, if applicable.

[0084] The concentration of VOCs measured in an enclosure can be used to: - adjust the flow rate of the air circulating within said enclosure; and / or - to start or stop the flow of air within said enclosure; and / or - trigger an alert, or an emergency stop of the heating stage, and / or the compression stage, more generally of the extraction phase.

[0085] According to embodiments, the method according to the invention may further include an adjustment of the flow rate of the, or of a, flow circulating in the enclosure, or in at least one enclosure.

[0086] This flow rate adjustment can be made according to different parameters, such as for example the temperature in the enclosure, the number of batteries in the enclosure, etc.

[0087] Following an example embodiment, this flow rate adjustment can be carried out as a function of a measured VOC concentration, as described above.

[0088] According to embodiments, the method according to the invention may further include an adjustment of the temperature of the flow, or of a flow, circulating in the enclosure, or in at least one enclosure.

[0089] This temperature adjustment can be made according to different parameters, such as for example the temperature in the enclosure, the number of batteries in the enclosure, etc.

[0090] Following an example embodiment, this temperature adjustment can be carried out as a function of a concentration of VOCs measured in the enclosure, as described above.

[0091] The compression step forces the molten lithium to evacuate from the battery.

[0092] The compression step can be carried out continuously throughout the extraction phase. In this case, the battery is subjected to compression, in part or in full, throughout the extraction phase, and in particular during the heating step.

[0093] Alternatively, the compression step can be carried out after the heating step, i.e. when the heating step is completed.

[0094] The compression step can apply compression to the surface of the battery by sweeping the surface of said battery from the second edge where the positive electrodes of said battery protrude, towards the first edge where the negative electrodes of said battery protrude. Thus, the molten lithium is gradually brought / guided towards the first edge where the negative electrodes protrude, which increases the amount of lithium recovered and reduces the risk of contact (or short circuit) between the lithium and the positive electrodes.

[0095] For example, the compression step can be carried out by passing the battery between two rollers, in particular two heated rollers.

[0096] Following another example, the compression step can be carried out by a compression roller, in particular heated, compressing the battery against a support surface, in particular heated.

[0097] Compression can be applied by successive passes, each pass sweeping the surface of the battery starting from the second edge towards the first edge.

[0098] The space between the compression rollers, or between the compression roller and the bearing surface, can correspond to the thickness of the battery minus the thickness of the metallic lithium layers. This allows compression to be applied as long as metallic lithium remains in the battery.

[0099] The space between the two compression rollers, respectively between the compression roller and the bearing surface, can be reduced with successive passes, so as to always apply compression to the battery.

[0100] The speed of passage between the compression rollers, respectively of the compression roller, and more generally the scanning speed, can be between a few mm and a few tens of mm per second.

[0101] According to embodiments, the process according to the invention may further include, before the extraction phase, an electrical charging step of the battery, said extraction phase being applied to said charged battery.

[0102] Electrically charging the battery and performing the extraction phase on the electrically charged battery increases the lithium extraction yield. Indeed, the electrical charging of a cell allows lithium ions to move towards the negative electrode, thus increasing the amount of lithium that can be recovered.

[0103] In the case where the battery comprises several cells, the method according to the invention may further include a step of breaking the electrical connection between the positive electrodes of at least two, and in particular of all, the cells of said battery. Thus, the electrical connection between the cells is broken, which reduces the risk of fire or ignition.

[0104] According to one embodiment, the cutting step can perform a cutting of connecting wires between the positive electrodes along a cutting line located at the level, and in particular at the limit, of the second border, on the side of said electrical connecting wires.

[0105] This embodiment makes it possible to retain, or not remove, solid metallic lithium from the battery, when the electrical connections are cut off, which makes it possible to improve the lithium recovery efficiency.

[0106] In this embodiment, the cutting of the connecting wires must be sufficiently close to the second edge, so that after the cutting, there is no longer any contact between the different positive electrodes.

[0107] According to another embodiment, the cutting step can perform a cutting of the cells along a cutting line located at the level, and in particular at the limit, of the second border, on the side of the cells.

[0108] In this embodiment, in order to reduce the amount of lithium lost, the cut must be in the immediate vicinity of the second edge.

[0109] For example, the cut can be made at a distance "d" from the second edge less than or equal to 2mm, or less than or equal to 1% of the cell dimension between the first and second edges of the battery.

[0110] The cutting step can be carried out by cutting. In this case, the battery can be inserted into a cutter of suitable size and power.

[0111] The switching-off step can be carried out before the heating step.

[0112] In addition, the method according to the invention may include, before the extraction phase, a step of removing at least one electrical connector from the battery, also called a "crimp" in English.

[0113] This makes battery processing easier.

[0114] For example, the step of removing at least one electrical connector from the battery may include a step of removing at least one negative connector, also called the "crimp anode". This facilitates / improves the flow of molten lithium out of the cell.

[0115] For example, the step of removing at least one electrical connector from the battery may include a step of removing at least one positive connector, also called "crimp cathode".

[0116] In addition, the process according to the invention may include, before the extraction phase, a step of removing excess material at the level of at least one, and particularly each, edge of the battery.

[0117] According to embodiments, the method according to the invention may further include a step of positioning the battery in an orientation in which the first border is below the second border.

[0118] Such an orientation of the battery, and therefore of each cell of the battery, makes it possible on the one hand to facilitate the flow of molten lithium out of the cell by gravity, and on the other hand to avoid contact between the molten lithium and the positive electrodes or the current collector of the positive electrode, such contact being able to cause an electrical short circuit or an electric arc, such a short circuit being able to cause a fire.

[0119] According to a preferred embodiment of this first version, the positioning step can perform a vertical positioning of the battery, in which the first edge is at the bottom.

[0120] Thus, the flow of molten lithium out of each cell, by gravity, is improved.

[0121] Furthermore, the risk of contact between the molten lithium and the positive electrode(s) is reduced, or even eliminated.

[0122] According to another aspect of the same invention, a lithium extraction system is proposed for an electric battery comprising metallic lithium, said system comprising, at least in part, arranged in one or more enclosures: - at least one heating means configured to heat said battery to a temperature, called the processing temperature, greater than or equal to the melting temperature of said metallic lithium; - at least one means of compressing said battery to evacuate the molten lithium out of the battery; said system further comprising: - at least one means of circulating a flow within said enclosure or within at least one of said enclosures; - at least one means of utilizing at least part of the energy from the outgoing flow of said enclosure or at least one of said enclosures.

[0123] Generally, the system according to the invention may include, in terms of technical means, or hardware configuration and / or software configuration, at least one, or any combination of at least two, of the optional features described above with reference to the method according to the invention.

[0124] According to embodiments, the system according to the invention may include a common enclosure in which the heating and compression of the battery are carried out.

[0125] According to embodiments, the system according to the invention may include a separate enclosure, called a heating enclosure, in which the heating of the battery is carried out.

[0126] According to embodiments, the system according to the invention may include a separate enclosure, called a compression enclosure, in which the compression of the battery is carried out.

[0127] According to embodiments, the system according to the invention may include a separate enclosure, called a cooling enclosure, in which the battery is cooled.

[0128] According to some embodiments, the heating chamber can be used to heat several batteries at once.

[0129] According to embodiments, the system according to the invention may include a heating chamber for several compression chambers.

[0130] In this case, at least two batteries heated in the same heating chamber can be compressed in different compression chambers.

[0131] According to embodiments, the cooling enclosure can be used to cool several batteries at once.

[0132] According to embodiments, at least part of the flow exiting the enclosure, or at least one enclosure, can be recirculated, or reinjected into said enclosure or into at least one enclosure.

[0133] In this case, the outgoing flow is reinjected into the enclosure, or at least one of the enclosures, to be reused in the process according to the invention and thus exploit the thermal energy of said outgoing flow.

[0134] For example, the outgoing flow can be reused as a heating flow and / or as an exhaust flow in the enclosure, or in at least one of the enclosures used in the process according to the invention.

[0135] In this case, according to an advantageous feature, the recovery means may include a means of removing at least part, or all, of the VOCs found in said outgoing stream, before recirculation / reinjection of said outgoing stream.

[0136] According to some embodiments, the VOC removal means can trap or filter VOCs. For example, the removal means can be a carbon filter or a carbon column, filtering VOCs as the outgoing stream passes through it.

[0137] According to embodiments, the recovery means may include a means of combustion, or oxidation, of at least a part of the VOCs found in the outgoing stream.

[0138] Such a means of combustion can be a burner.

[0139] According to embodiments, the recovery means may include a means of storing at least part of the heat from the outgoing stream, possibly after combustion of VOCs.

[0140] Such a storage means may include a tank, in particular thermally insulated, of heat transfer fluid, FCA, such as water or oil, to which said heat is transferred.

[0141] According to some embodiments, the means of valorization may include a means of heating an incoming flow into an enclosure, by heat transfer between the outgoing flow and said incoming flow.

[0142] Such a means of heating may be a heat exchanger, a heat pump, etc.

[0143] The, or at least one, means of circulation may include a blowing means and / or a suction means.

[0144] According to some embodiments, the, or at least one, means of circulation may be adjustable / controllable to adjust: - the flow rate, and / or - the temperature; of the flow circulating within the enclosure, or within at least one enclosure.

[0145] The adjustment can be made based on a measured temperature, or a measured concentration of VOCs.

[0146] According to embodiments, the system according to the invention may include at least one gas sensor for measuring the concentration of at least one volatile organic compound, VOC.

[0147] When the heating and compression of the battery are carried out in a common enclosure, at least one measuring means may be disposed in said common enclosure, or at least equip said common enclosure.

[0148] When the heating and compression of the battery are carried out in separate enclosures, namely a heating enclosure and a compression enclosure, then the system according to the invention may include - at least one sensor fitted to the heating chamber, and / or - at least one sensor fitted to the compression chamber.

[0149] The compression means can be in any form.

[0150] According to embodiments, the compression means may include at least one roller, in particular a heated one.

[0151] In particular, the compression means may comprise a single roller, in particular a heated roller, compressing the battery against a support surface, in particular a heated surface. The support surface may be heated to accelerate the temperature rise of the battery.

[0152] Alternatively, the compression means may comprise two rollers, in particular heated rollers, between which the battery is passed.

[0153] In general, the compression means can be configured to apply continuous compression throughout the extraction phase.

[0154] Alternatively, the compression means can be configured to apply compression discretely over time, once or several times, during the extraction phase. In this case, the extraction phase includes moments when the battery is not subjected to compression.

[0155] Advantageously, the compression means can be configured to apply compression, of constant or variable value, progressively or by sweeping across the surface of the battery, from the second edge to the first edge. Thus, the molten lithium is gradually brought / guided towards the first edge, which is in the lower position, thereby increasing the amount of lithium recovered and reducing the risk of contact between the lithium and the positive electrodes.

[0156] When using one or two compression rollers, compression can be applied to the battery in successive passes. Each pass applies sweeping compression to the battery surface, from the second edge to the first edge. At the end of each pass, compression can be stopped by moving the rollers apart or by moving the roller away from the support surface, returning to the second edge to begin a new pass.

[0157] The distance between the rollers, respectively between the compression roller and the bearing surface, can be decreased as the passes progress, and in particular between two successive passes.

[0158] According to embodiments, the system according to the invention may further include a means for breaking the electrical connection between the positive electrodes of at least two, and in particular of all the cells of said battery.

[0159] For example, the cutting means may include a guillotine. Description of the figures and methods of realization

[0160] Other advantages and features will become apparent upon examination of the detailed description of non-limiting embodiments and the accompanying drawings, in which: - [Fig.1] is a schematic representation of a non-limiting example embodiment of a cell within the meaning of the present invention; - [Fig.2] is a schematic representation of a non-limiting example of a battery within the meaning of the present invention; - the [Fig.3]-5 are schematic representations of non-limiting examples of embodiments of a process according to the invention; - FIGURES 6a-6c are schematic representations of a non-limiting example embodiment of a system according to the present invention; - FIGURES 7a-7c are schematic representations of another non-limiting example of an embodiment of a system according to the present invention; - Figures 8a-8c are schematic representations of another, non-limiting embodiment of a system according to the present invention; and - FIGURES 9a-9c are schematic representations of non-limiting examples of a valorization unit that can be implemented in the present invention.

[0161] It is understood that the embodiments described below are in no way limiting. In particular, variants of the invention may be conceived comprising only a selection of the features described below, isolated from the other features described, if this selection of features is sufficient to confer a technical advantage or to differentiate the invention from the prior art. This selection includes at least one preferably functional feature without structural details, or with only a portion of the structural details if this portion is sufficient solely to confer a technical advantage or to differentiate the invention from the prior art.

[0162] In the figures, the elements common to several figures retain the same reference.

[0163] Fig. 1 is a schematic representation of a non-limiting example embodiment of a cell within the meaning of the present invention.

[0164] The cell 100, shown in [Fig.1], includes a negative electrode 102. According to a non-limiting embodiment, the negative electrode 102 is formed by, or comprises, a layer of solid metallic lithium.

[0165] The cell 100 further comprises a positive electrode 104. According to a non-limiting embodiment, the positive electrode 104 is formed by a polymer-based layer and active material.

[0166] A layer 106 of electrolyte is disposed between the negative electrode 102 and the positive electrode 104. According to a non-limiting embodiment, this solid electrolyte layer 106 may, for example, comprise lithium salts.

[0167] The cell 100 further includes a current collector 108, on the side of the positive electrode 104. According to a non-limiting embodiment, the current collector 108 can be made of aluminum.

[0168] According to a non-limiting architecture, in the example of [Fig.1], the negative electrode 102 of the cell 100 protrudes from the other elements of the cell 100 on the side of a first border 110 of the cell 100. Also according to the non-limiting architecture of [Fig.1], the positive electrode 104, and / or the collector 108, of the cell 100 protrudes from the other elements of the cell 100 on the side of a second border 112, opposite to the first border 110.

[0169] Of course, cell 100 shown in [Fig. 1] is a very simplified embodiment, given by way of non-limiting illustration. The cell within the meaning of the present invention may comprise a multitude or a succession of several anode / electrolyte / cathode layers, or at least one other layer than those indicated, or at least one layer whose composition differs from the composition given here by way of non-limiting example.

[0170] Fig. 2 is a schematic representation of a non-limiting example embodiment of a battery within the meaning of the present invention.

[0171] A battery according to the present invention may comprise one or more cells, and in particular one or more cells 100 of the [Fig.1].

[0172] In the example shown in [Fig.2], the battery 200 comprises n cells 100r 100n, with n>l.

[0173] All 100r100n cells can be identical.

[0174] The cells 100i-100n are assembled along a direction 202 perpendicular to the plane of each cell 100;.

[0175] Each cell 100;, with l <i<n, peut être identique à la cellule 100 de la [Fig. 1].

[0176] Of course, the battery 200 may include other components than those shown in [Fig.2] which gives a simplified schematic representation of a battery.

[0177] In the following, and without loss of generality, the battery is considered to comprise several cells assembled along an assembly direction.

[0178] Fig. 3 is a schematic representation of a non-limiting example of an embodiment of a method according to the present invention.

[0179] The process 300 of [Fig.3] can be used to recover lithium from a battery comprising lithium, in particular metallic lithium, and even more particularly from battery 200 of [Fig.2].

[0180] The process 300 includes a phase 302 of lithium extraction from the battery by heating and compression of the battery.

[0181] The extraction phase 302 includes a step 304 of heating the battery. The heating of the battery can be carried out in different ways.

[0182] In the embodiment shown in [Fig. 3], the battery is heated in a chamber, referred to as a heating chamber. More specifically, the battery is placed in a closed heating chamber heated with one or more radiant heating plates. In practice, the battery is positioned between two heating plates placed on either side of the battery parallel to the surface of the cells, and in particular in contact with the battery. Thus, the battery temperature is raised to a processing temperature of 185°C or higher. At this temperature, the lithium in the battery begins to melt and is ready to flow out of the battery.

[0183] The extraction phase 302 then includes a step 306 of compressing the heated battery to force the molten metallic lithium, contained in the heated battery, to evacuate out of said battery.

[0184] In the embodiment shown in [Fig. 3], the battery compression is carried out in a chamber, referred to as a compression chamber. More specifically, the battery, heated to at least 185°C, is placed in a compression chamber equipped with compression means. It is then compressed perpendicular to the plane of the cells to force the molten lithium out of the battery. The molten lithium is collected, for example, in a tray or container positioned under the battery.

[0185] The battery compression can be achieved in various ways. According to one embodiment, the heated battery is passed between two rollers, in particular heated rollers, which apply compression to the surface of the battery by sweeping over the surface of said battery, for example, by going from the second edge 112 to the first edge 110 from which the negative electrodes 102 protrude. cells of said battery. Thus, the molten lithium is gradually brought / guided towards the first edge and then exits the battery through the first edge.

[0186] Optionally, the extraction phase 302 may include, after the compression step 306, a battery cooling step 308.

[0187] Cooling can be achieved in various ways, for example by leaving the battery at room temperature for a sufficient period of time.

[0188] In the embodiment shown in [Fig. 3], the battery is cooled in an enclosure, referred to as the cooling enclosure. More specifically, the hot battery is placed in a cooling enclosure through which a flow, referred to as the cooling flow, denoted FR, circulates.

[0189] Without limitation, the cooling flow FR may be a neutral gas flow, such as argon (Ar), for example at room temperature or at a temperature below room temperature.

[0190] The cooling flow FR is introduced into the enclosure in which the cooling step 308 is carried out, circulates within said enclosure to come into contact with the battery to be cooled and absorbs thermal energy, then exits the enclosure heated. In the following, FRe denotes the cooling flow entering the enclosure and FRs denotes the cooling flow exiting the enclosure.

[0191] Without limitation, the heating and compression chambers may be separate: in this case, these chambers may be in contact with each other, or at a distance from each other. Alternatively, the heating and compression chambers may be a single, common chamber.

[0192] Without limitation, the compression and cooling chambers may be separate: in this case, these chambers may be in contact with each other, or at a distance from each other. Alternatively, the compression and cooling chambers may be a single, common chamber.

[0193] The invention is not limited to any particular enclosure architecture.

[0194] In the non-limiting example of [Fig.3], the process 300, and in particular the extraction phase 302, may further include a step 314 of circulation of a flow, called first evacuation flow, noted FE1 during the heating step 304. This first evacuation flow FE1 allows the VOCs released by the battery during the heating step 304 to be evacuated from the enclosure.

[0195] This evacuation of VOCs can be carried out during the entire duration of the heating step 304, or only part of the heating step 304. Without limitation, the first evacuation flow FE1 can be a neutral gas flow, such as argon (Ar).

[0196] The first exhaust flow FE1 is introduced into the enclosure in which the heating step is carried out, circulates in said enclosure to come into contact with the The battery, during heating, absorbs the VOCs released by the battery as well as thermal energy, then exits the enclosure laden with VOCs and hot. In the following, FE1 denotes the first exhaust flow entering the enclosure and FE1 denotes the first exhaust flow exiting the enclosure.

[0197] Alternatively, or in addition, in the non-limiting example of [Fig.3], the process 300, and in particular the extraction phase 302, may include a step 316 of circulation of a flow, called second evacuation flow, denoted FE2 during the compression step 306. This second evacuation flow FE2 allows the VOCs released by the battery during the compression step 306 to be evacuated from the enclosure.

[0198] This evacuation of VOCs can be carried out during the entire duration of the compression step 306, or only part of the compression step 306. Without limitation, the second evacuation stream FE2 can be a neutral gas stream, such as argon (Ar).

[0199] The second exhaust stream FE2 is introduced into the chamber in which the compression step 306 is carried out, circulates within said chamber to come into contact with the battery being compressed, becomes charged with VOCs released by the battery as well as with thermal energy since the battery is very hot, and then exits the chamber charged with VOCs and hot. In the following, FE2e denotes the second exhaust stream entering the chamber and FE2s denotes the second exhaust stream exiting the chamber.

[0200] According to a feature not shown, the extraction phase 302 may include a measurement of the VOC concentration in the heating chamber. For example, this measurement may be carried out at a fixed frequency or continuously. The measured concentration may be used to start / stop step 314, or to adjust the flow rate of the first exhaust flow FE1 during step 314, or for an emergency shutdown.

[0201] According to a feature not shown, the extraction phase 302 may include a measurement of the VOC concentration in the compression chamber. For example, this measurement may be performed at a fixed frequency or continuously. The measured concentration may be used to start / stop step 316, or to adjust the flow rate of the second exhaust stream FE2 during step 316, or for an emergency shutdown.

[0202] Advantageously, the process 300 includes a step 320 for recovering at least some of the energy from at least one of the output streams of the enclosure, or at least one of the enclosures, used during the extraction phase 302. For example, the recovery step 320 may recover / recover at least some of the energy: of the FEls flow exiting the heating chamber, and / or of the FE2s flow exiting the compression chamber, and / or

[0203]

[0204]

[0205]

[0206]

[0207]

[0208] - of the FRs flow exiting the cooling chamber. Recovery step 320 may include combustion or oxidation of at least some of the VOCs in the outgoing stream. For example, recovery step 320 may include combustion or oxidation of at least some of the VOCs in: - the FEls flow exiting the heating chamber, and / or - the FE2s flow exiting the compression chamber, and / or - possibly, the FRs flow exiting the cooling enclosure. The recovery step 320 may include using at least some of the energy recovered from an outgoing stream to heat at least one incoming stream into the enclosure, or one of the enclosures, used during the extraction phase 302. For example, the recovery step 320 may use at least some of the recovered energy to heat: - the FEle flow entering the heating chamber, and / or - the FE2e flow entering the compression chamber; regardless of the outgoing flow from which said energy was recovered. The recovery step 320 may include a heat exchange between an outgoing stream and an incoming stream to heat the incoming stream, possibly after combustion / oxidation of VOCs present in the outgoing stream. For example, the recovery step 320 may include a heat exchange between: - any one of the outgoing flows FEls, FE2s and FRs; and - any one of the incoming flows FE1, FE2e. Heat exchange can be achieved by any known means, such as for example a heat exchanger, a heat pump circuit, etc. The recovery step 320 may include storing at least some of the energy from at least one outgoing stream, for example in a tank designed for this purpose. In particular, some of the energy from at least one outgoing stream may be used to heat a heat transfer fluid, denoted FCA, such as oil, stored in a tank. For example, the recovery step 320 may include a heat exchange between: - any one of the outgoing flows FEls, FE2s and FRs; and - the FCA heat transfer fluid; stored in an insulated tank. This heat transfer fluid FCA can then be used to heat at least one of the incoming streams FEle, FE2e or any other fluid used in the process according to the invention or in another installation. The 320 recovery step may include recirculation of at least part of the outgoing stream into the enclosure, or into at least one enclosure, used during the extraction phase.

[0209] In this case, the recovery step may include, before recirculation / reinjection of the outgoing stream into said enclosure, the removal of at least some, or all, of the VOCs present in said outgoing stream. The VOCs in the outgoing stream may be removed using any known technique. According to exemplary embodiments, the VOCs in the outgoing stream may be removed by trapping said VOCs, for example with a carbon filter or a carbon column. In this case, the outgoing stream passes through said carbon filter or column, which retains the VOCs and thus allows the removal of some or all of the VOCs present in said outgoing stream.

[0210] Fig. 4 is a schematic representation of another non-limiting embodiment of a method according to the present invention.

[0211] The process 400 of [Fig.4] can be used to recover lithium from a battery comprising lithium, in particular metallic lithium, and even more particularly from battery 200 of [Fig.2].

[0212] The process 400 of [Fig.4] includes a lithium extraction phase 402 comprising all the steps of the extraction phase 302 of the process 300 of [Fig.3], except the first evacuation stream circulation step 314 FE1.

[0213] In process 400, the heating step 304 is carried out by circulating a gaseous flow, referred to as the heating flow and hereafter denoted FC, within the heating chamber. This heating flow FC may be at a temperature greater than or equal to the processing temperature, i.e., greater than or equal to 185°C. The heating flow FC circulating within the chamber in which the heating step is carried out serves both to heat the coil and to remove the VOCs released by the coil during said heating step. In other words, the heating flow FC, in addition to heating the coil, acts as the first exhaust flow and ventilates the chamber in which the heating step is carried out.

[0214] The heating flow FC is introduced into the enclosure in which the heating step is carried out, circulates within said enclosure to come into contact with the battery and heat it, and may become charged with VOCs released by the battery, then exits the enclosure laden with VOCs. In the following, FCe denotes the heating flow FC entering the enclosure and FCs denotes the heating flow FC exiting the enclosure.

[0215] The process 400 of [Fig.4] includes the recovery step 320 as described above, replacing, in the description of said step, the first evacuation flow with the heating flow, i.e. FE1 with FC, FEle with FCe and FEls with FCs.

[0216] In the examples described with reference to FIGURES 3 and 4, the valorization step 320 is not part of the extraction phase 302 or 402. Of course, Alternatively, the valuation step 320 can be part of the extraction phase 302 or 402.

[0217] According to another alternative not shown, the invention may not include a VOC venting system from the heating chamber. Indeed, the inventors have observed that, during the heating stage, the battery releases fewer VOCs compared to the compression stage.

[0218] According to another alternative not shown, the VOC evacuation step 316 can be carried out / triggered at the beginning or end of the compression step 306, and / or continue after the end of the compression step 306.

[0219] Fig. 5 is a schematic representation of another non-limiting embodiment of a method according to the present invention.

[0220] The process 500 of [Fig.5] can be used to recover lithium from a battery comprising lithium, in particular metallic lithium, and even more particularly from battery 200 of [Fig.2].

[0221] The process 500 includes an optional step 502, which performs an electrical recharging of the battery. The battery can be partially or fully charged. Electrically charging the battery increases the amount of lithium available for extraction because the recharging causes lithium ions to migrate from each battery cell to the negative electrode of that cell.

[0222] The process 500 includes an optional step 504 of breaking the electrical connection between the positive electrodes of at least two, and in particular all, of the cells of said battery. Thus, the electrical connection between the cells is broken, which reduces the risk of fire or ignition.

[0223] The process 500 includes an optional step 506 for removing electrical connectors, and in particular current concentrators, also known as "crimps." Specifically, step 506 removes the anode crimps to facilitate the flow of molten lithium from each cell, and optionally removes the cathode crimps. Optionally, step 506 may also remove excess material, and in particular solid metallic lithium, from each lateral edge of the battery.

[0224] The method 500 further includes an optional but highly advantageous step 508 for positioning the battery in an orientation in which the first edge, 110 in the example of battery 200, from which the negative electrodes protrude, is at a lower level than the second edge, 112 in the example of battery 200, from which the positive electrodes and collectors protrude. In particular, step 508 positions the battery in a vertical orientation, i.e., parallel to the gravity vector, with the first edge at the bottom. Preferably, but of In no way limiting, the battery is maintained in this orientation throughout the entire extraction phase.

[0225] Next, the process 500 comprises an extraction phase 510, such as for example extraction phase 302 or 402, and a valorization step 320 described with reference to FIGURES 3 and 4, said valorization step 320 being able to form part of, or not of, said extraction phase 510.

[0226] FIGURES 6a-6c are schematic representations of a non-limiting example embodiment of a system according to the present invention.

[0227] The 600 system of FIGURES 6a-6c can be used to recover lithium from a battery comprising lithium, in particular metallic lithium, and even more particularly from battery 200 of [Fig.2].

[0228] System 600 can be used to implement a process according to the invention, for example any one of the processes 300, 400 or 500.

[0229] The system 600 includes a heating chamber 602 in which the battery 200 is heated and a compression chamber 604 in which the battery 200 is compressed, and optionally a cooling chamber 606 for the battery 200 after lithium extraction.

[0230] In [Fig. 6a], battery 200 is located in the heating chamber 602, on the [Fig.6b] Battery 200 is located in the compression chamber 604 and on the [Fig.6c] Battery 200 is located in the optional cooling chamber 606.

[0231] During its processing in the system 600, the battery 200 is placed on a support 608.

[0232] The support 608 allows the battery 200 to be positioned and held in an orientation in which the first edge 110, from which the negative electrodes protrude, is below the level of the second edge 112, from which the positive electrodes protrude. In the example in FIGURE 6, the support 608 holds the battery 200 in a vertical position with the first edge 110 at the bottom and the second edge 112 at the top.

[0233] In addition, the support 608 is equipped with a receptacle 610 for receiving the molten lithium metal. In particular, the molten lithium metal exiting the battery 200 flows out of said battery 200 and then towards the receptacle 610 under the effect of gravity and is collected in said receptacle 610.

[0234] In embodiments, the support 608 and the receptacle 610 can be formed from a single piece, or a single component.

[0235] The heating chamber 602 is equipped with a heating means for the battery 200 to raise the battery 200 to a processing temperature greater than or equal to the melting point of metallic lithium, for example greater than or equal to 185°C. In the example of FIGURES 6a-6c, the heating means comprises two Heating plates 612, between which the battery is placed, come into contact with said battery 200 to heat it. In particular, the battery 200 is positioned between the heating plates 612 so that said battery 200 is heated on each of its faces. For example, the heating plates 612 are electric plates.

[0236] The heating chamber 602 is equipped with a first circulation means for a first flow, namely the first exhaust flow, FE1, mentioned above. In particular, the first circulation means comprises: - an inlet duct 614i in the heating chamber 602 of the FEle flow, - an outlet duct 6142 from the heating chamber 602 of the FEls flow, and - a means of training 6143 of the FE1 flow, such as for example a fan, blower, etc. Thus, the heating chamber 602 receives the FEle flow through the inlet duct 614i. The FEle flow sweeps through the heating chamber 602, and in particular the battery 200 located within the chamber 602. The FEle flow exits through the outlet duct 6142 carrying some or all of the VOCs present in the heating chamber 602.

[0237] The FE1 flow can be a dry air flow or a neutral gas flow, such as argon (Ar). The FE1 flow can be at ambient temperature or at a temperature higher than ambient temperature, for example on the order of 60°C.

[0238] Optionally, the heating chamber 602 can be equipped with a sensor 616 to measure the VOC concentration within said chamber 602. This sensor 616 can be configured to measure the VOC concentration continuously or at a predetermined frequency. The concentration measured by the sensor 616 can be used to start, stop, or adjust the circulation of the FE1 flow, either directly or through a control module (not shown). In this case, the drive means 6143 can be controllable / adjustable. The concentration measured by the sensor 616 can be used to adjust the temperature of the FE1 flow. The concentration measured by the sensor 616 can be used to trigger an emergency shutdown of the system 600, and in particular of the heating system.

[0239] Of course, the heating enclosure 602 may include other component(s) than those described here.

[0240] In the compression chamber 604, the battery 200 is held by the support 608 as described above.

[0241] The compression chamber 604 is equipped with a battery compression means for forcing the molten metallic lithium out of said battery 200. In the example of FIGURES 6a-6c, the compression means comprises a pair of rollers 622, in particular heated, facing each other. The battery 200 is positioned between the rollers 622 in a vertical orientation in which the first edge 110 is below the second edge 112. The rollers 622 apply, in successive passes, compression to the battery 200 by sweeping the battery 200 from the second edge 112 to the first edge 110. Thus, the molten metallic lithium is expelled from the battery 200 through the first edge 110 and flows into the recovery receptacle 610. This example of a compression method is by no means limiting and other variations may be used.

[0242] The compression chamber 604 is equipped with a second means for circulating a flow, and in particular the second exhaust flow, FE2, of VOCs from said chamber 604, mentioned above. In the example of FIGURES 6a-6c, the second means of circulation comprises: - an inlet duct 624i in the compression chamber 604, of the FE2e flow; - an outlet duct 6242 from the compression chamber 604 of the FE2s flow; and - a means of driving said flow FE2, such as for example a fan, a blower, etc. Thus, the compression chamber 604 receives the FE2e flow through the inlet duct 624i. This flow sweeps through the compression chamber 604, and in particular the battery 200 located within it. The FE2s flow exits through the outlet duct 6242, carrying some or all of the VOCs present in the compression chamber 604.

[0243] The FE2 flow can be a dry air flow or a neutral gas flow, such as argon (Ar). The FE2 flow can be at ambient temperature or at a temperature higher than ambient temperature, for example around 60°C, or at the processing temperature so as not to cool the battery 200 during its compression.

[0244] Optionally, the compression chamber 604 can be equipped with a sensor 626 to measure the VOC concentration within said chamber 604. This sensor 626 can be configured to measure the VOC concentration continuously or at a predetermined frequency. The concentration measured by the sensor 626 can be used to start, stop, or adjust the flow of the FE2 stream within the compression chamber, either directly or via a control module (not shown). In this case, the drive means 6243 can be controllable / adjustable. The concentration measured by the sensor 626 can be used to adjust the temperature of the FE2 stream. The concentration measured by the sensor 626 can be used to trigger an emergency shutdown of the system 600, and in particular, of the compression.

[0245] Of course, the compression chamber 604 may include other component(s) than those described here.

[0246] In the optional cooling enclosure 606, the battery 200 can be held by the bracket 608 as described above.

[0247] The cooling of the battery 200 in the cooling enclosure 606 can be achieved in any known or suitable manner, for example by circulating a cooling flow, namely the cooling flow FR mentioned above. For this purpose, the cooling enclosure 606 is equipped with a third flow circulation means. In the example of FIGURES 6a-6c, the third circulation means comprises: - an inlet duct 634i in the cooling enclosure 606, of the FRe flow; - an outlet duct 6342 from the cooling chamber 606 of the FRs flow; and - a means of driving said cooling flow FR, such as for example a fan, a blower, etc. Thus, the cooling enclosure 606 receives the incoming cooling flow FRe through the inlet duct 634b. The latter sweeps through the cooling enclosure 606, and in particular the battery 200 located in the enclosure 606. The outgoing cooling flow FRs exits through the outlet duct 6342 carrying some of the heat from the battery being cooled.

[0248] The FR cooling flow can be a dry air flow or a neutral gas flow, such as argon (Ar). The FR cooling flow can be at ambient temperature or at a temperature lower than ambient temperature.

[0249] The 606 cooling enclosure can optionally be equipped with: - a sensor for measuring the concentration of VOCs (not shown); - a temperature measurement sensor to ensure that the cell is properly cooled before it comes out of the machine; in a similar or identical manner to what has just been described for the heating chamber 602 or for the compression chamber 604.

[0250] Of course, the cooling enclosure 606 may include other component(s) than those described here.

[0251] In system 600, the heating chamber 602, the compression chamber 604 and the optional cooling chamber 606 are separate from each other.

[0252] Furthermore, according to the invention, the system 600 includes a unit 640 for recovering at least part of the energy from at least one outgoing flow from at least one of the enclosures 602, 604 and 606, namely from at least one of the flows FEls, FE2s and FRs.

[0253] Non-limiting examples of such a valuation unit will be described later with reference to FIGURES 9a to 9c.

[0254] FIGURES 7a-7c are schematic representations of another non-limiting embodiment of a system according to the present invention.

[0255] The 700 system of FIGURES 7a-7c can be used to recover lithium from a battery comprising lithium, in particular metallic lithium, and even more particularly from battery 200 of [Fig.2].

[0256] System 700 can be used to implement a process according to the invention, for example any one of the processes 300, 400 or 500.

[0257] System 700 is identical to system 600 in FIGURES 6a-6c except for the differences indicated below.

[0258] Unlike system 600, in system 700 the heating of the battery in the heating chamber is achieved not by using heating plates but by circulating a heating flow, for example the FC heating flow mentioned above. Thus, the heating chamber 602 of system 700 does not include heating plates 612.

[0259] The first circulation means equipping the heating chamber 602 is used to circulate the heating flow FC within the heating chamber. Thus, the heating chamber 602 receives the incoming heating flow FCe through the inlet duct 614b. This flow sweeps through the heating chamber 602, and in particular the coil 200 located within the chamber 602, to heat it and potentially absorb the VOCs released by the coil 200. The outgoing heating flow FCs exits through the outlet duct 6142, carrying some or all of the VOCs present in the heating chamber 602.

[0260] The heating flux FC can be a dry air flow or a neutral gas flow, such as argon (Ar). The heating flux FC is at the processing temperature or higher.

[0261] Sensor 616 can be configured to measure VOC concentration continuously or at a predetermined frequency. The concentration measured by sensor 616 can be used to start, stop, or adjust the circulation of the heating flow FC in the heating chamber 602, either directly or via a control module (not shown). In this case, the drive means 6143 can be controllable / adjustable. The concentration measured by sensor 616 can be used to adjust the temperature of the heating flow FC. The concentration measured by sensor 616 can be used to trigger an emergency shutdown of the system 700, and in particular, the heating system.

[0262] FIGURES 8a-8c are schematic representations of another non-limiting embodiment of a system according to the present invention.

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274] The 800 system of FIGURES 8a-8c can be used to recover lithium from a battery containing lithium, in particular metallic lithium, and even more particularly from the 200 battery of [Fig.2]. System 800 can be used to implement a process according to the invention, for example any one of processes 300, 400 or 500. Unlike systems 600 and 700, system 800 includes a single common enclosure 802 for heating and compressing battery 200. Optionally, system 800 can include the cooling enclosure 606 from systems 600 and 700, separate from the common enclosure 802. The common enclosure 802 is equipped with a means of circulating flow, and in particular the first means of circulation 614r6143 for circulating: - the first exhaust flow FE1, or the heating flow FC; and / or - the second evacuation flow FE2. Optionally, the common enclosure 802 can be equipped with a sensor for measuring the concentration of VOCs in said common enclosure 802, such as, for example, sensor 616. The common enclosure 802 includes a heating zone 804 comprising a means for heating the battery 200, for example the heating plates 612. Alternatively, the heating of the battery 200 can be achieved by a heating flow, FC, as in the system 700. The common enclosure 802 includes a compression zone 806 comprising a battery compression means 200, for example rollers 622. In [Fig.8a], battery 200 is located in heating zone 804, in [Fig.8b] battery 200 is located in compression zone 806 and in [Fig.8c] battery 200 is located in the optional cooling enclosure 606. System 800 also includes unit 640 for valuation. Of course, each of the 600, 700 and 800 systems may include other components than those described above, such as, for example: - a means of electrically recharging the 200 battery, and / or - a means of removing electrical connectors from said battery 200, and / or - a means of breaking the electrical connection between the positive electrodes of the 200 battery, and / or - etc. Figure 9a is a schematic representation of a non-limiting example embodiment of a valorization unit that can be implemented in the present invention. The 900 valorization unit of [Fig. 9a] can be used in a lithium extraction system from a battery containing lithium, in particular lithium metallic, and even more specifically of battery 200 of [Fig.2]. The 900 recovery unit of [Fig.9a] can be the 640 recovery unit of any of the 600, 700 or 800 systems.

[0275] The recovery unit 900 receives at least some output streams from the chamber, or from at least one of the chambers, used for the extraction phase, and in particular at least some FEls, FE2s, FCs, or FRs streams. In the following, and in [Fig. 9a], the reference FS designates an output stream which can be any one of the FEls, FE2s, FCs, or FRs streams.

[0276] The recovery unit 900 may optionally include a burner 902 for burning at least some of the VOCs present in the FS outlet stream, or at least one of them. For example, the burner 902 may be used to burn, particularly under air or pure oxygen, at least some of the VOCs present in the FEls stream and / or the FE2s stream and / or the FCs stream and / or the FRs stream, as appropriate. This combustion is exothermic and raises the temperature of said outlet stream.

[0277] The recovery unit 900 may include a heat exchange means 904 for transferring at least a portion of the heat from at least one output stream FS to at least one of the streams FE1, FE2e, or FCe entering the enclosure, or enclosures, used. In the following, and in [Fig. 9a], the reference numeral FE designates an input stream, which may be any one of the input streams FE1, FE2e, or FCe. For example, the heat exchange means may perform a heat exchange between: - any one of the outgoing flows FEls, FE2s, FCs and FRs; and - any one of the incoming flows FEle, FE2e and FCe.

[0278] The heat exchange means 904 may be, or include, at least one heat exchanger or heat pump.

[0279] Fig. 9b is a schematic representation of another non-limiting embodiment of a valorization unit that can be implemented in the present invention.

[0280] The recovery unit 910 of [Fig. 9b] can be used in a lithium extraction system for a battery containing lithium, in particular metallic lithium, and even more particularly battery 200 of [Fig. 2]. The recovery unit 910 of [Fig. 9b] can be the recovery unit 640 of any of the systems 600, 700 or 800.

[0281] Valuation unit 910 includes all the elements of valuation unit 900 of [Fig.9a], except with regard to the differences mentioned below.

[0282] The recovery unit 910 further includes an insulated reservoir 912 for a heat transfer fluid, denoted FCA, such as, for example, oil or water. In particular, the heat transfer fluid FCA may be Therminol®.

[0283] The heat exchange means 904 performs a heat exchange between at least one outlet stream FS and the heat transfer fluid FCA which is stored in the tank 912. For example, the heat exchange means 904 can perform a heat exchange between: - any one of the outgoing flows FEls, FE2s, FCs and FRs; and - the FCA heat transfer fluid stored in the tank. Thus, the heat recovered from any of the outgoing streams FEls, FE2s, FCs and FRs is stored in tank 912 and can be used either to heat any of the incoming streams FEle, FE2e and FCe or any other fluid used in the process / system according to the invention, or in another installation.

[0284] Fig. 9c is a schematic representation of another non-limiting embodiment of a valorization unit that can be implemented in the present invention.

[0285] The recovery unit 920 of [Fig. 9c] can be used in a lithium extraction system for a battery comprising lithium, in particular metallic lithium, and even more particularly battery 200 of [Fig. 2]. The recovery unit 920 of [Fig. 9c] can be the recovery unit 640 of any of the systems 600, 700 or 800.

[0286] The recovery unit 920 includes a VOC removal unit 922 for the outgoing stream FS in order to reuse said outgoing stream FS as an incoming stream FE in the chamber(s). In other words, the VOCs are removed, at least partially, from the outgoing stream and the outgoing stream FS is reused / reinjected as an incoming stream FE in one of the chambers.

[0287] The VOC removal unit 922 may, for example, be a carbon filter or a carbon column through which the outgoing stream FS passes. The VOC removal unit 922 may, for example, be any other means of VOC removal, for example a burner.

[0288] Of course, the invention is not limited to the detailed examples above.

Claims

Demands

1. A process (300;400;500) for extracting lithium from an electric battery (200) comprising metallic lithium, said process (300;400;500) comprising a lithium extraction phase (302;402;510), carried out, at least in part, in one or more enclosures (602-606;802,606), said extraction phase (302;402;510) comprising the following steps: - heating (304) of said battery (200) to a temperature, referred to as the processing temperature, greater than or equal to the melting temperature of metallic lithium; - compressing (306) of said battery (200) to remove the molten lithium from the battery (200); said extraction phase (302;402;510) further comprising a circulation of a flow in said enclosure (602-606;802,606), or in at least one of said enclosures (602-606;802,606); said process (300;400;500) further comprising a recovery (320) of at least a part of the energy of the flow exiting said enclosure (602-606;802,606), or at least one of said enclosures (602-606;802,606).;

2. A process (300;500) according to the preceding claim, characterized in that the lithium extraction phase (302;402;510) includes a circulation of a flow (FE1), referred to as the first evacuation flow, during the heating step (304), in particular to evacuate at least a part of the VOCs released by the battery (200) during said heating step (304).

3. Method (400;500) according to claim 1, characterized in that it comprises a circulation, during the heating step (304), of a flow (FC), called heating flow, to heat the battery (200).

4. A method (300;400;500) according to any one of the preceding claims, characterized in that it comprises a circulation of a flow (FE2), called a second evacuation flow, during the compression step (306), in particular to evacuate at least a part of the VOCs released by the battery (200) during said compression step (306).

5. A method (300;400;500) according to any one of the preceding claims, characterized in that: - the heating stage (304) and the compression stage (306) are carried out in the same enclosure (802); or - the heating stage (304) is carried out in an enclosure (602), called the heating enclosure, and the compression stage (306) is carried out in an enclosure (604), called the compression enclosure, separate from said heating enclosure (602).

6. A method according to any one of the preceding claims, characterized in that the recovery step (320) includes a recirculation of at least a part of the outgoing stream into the enclosure (602-606;802,606), or into at least one of the enclosures (602-606;802,606).

7. A method according to the preceding claim, characterized in that it comprises, prior to recirculation, the removal of at least some, or all, of the VOCs found in said outgoing stream.

8. A process (300;400;500) according to any one of the preceding claims, characterized in that the recovery step (320) comprises a combustion, or an oxidation, of at least part of the VOCs found in the outgoing stream (FS;FEls,FE2s,FRs;FCs).

9. A process (300;400;500) according to any one of the preceding claims, characterized in that the recovery step (320) includes a storage of at least a part of the heat from the outgoing stream (FS;FEls,FE2s,FRs;FCs), optionally after combustion of VOCs.

10. A process (300;400;500) according to any one of the preceding claims, characterized in that the valorization step (320) comprises heating an incoming stream (FE;FEle,FE2e;FCe) in an enclosure (602,604;802), by heat transfer between the outgoing stream (FS;FEls,FE2s,FRs;FCs) and said incoming stream (FE;FEle,FE2e;FCe).

11. Method (300;400;500) according to the preceding claim, characterized in that the incoming flow (FE;FEle,FE2e;FCe) and the outgoing flow (FS;FEls,FE2s,FRs;FCs) concern the same enclosure or different enclosures.

12. System (600;700;800) for extracting lithium from an electric battery (200) comprising metallic lithium, said system (600;700;800) comprising, at least partly arranged in one or more enclosures (602-606;802,606): - at least one heating means (612;614i-6143) configured to heat said battery (200) to a temperature, called the processing temperature, greater than or equal to the melting temperature of said metallic lithium; and - at least one compression means (622) of said battery (200) to evacuate the molten lithium out of the battery (200); the system further comprising: - at least one circulation means (614i-6143,624i-6143,634i-6143) of a flow in said enclosure or in at least one of said enclosures (602-606;802,606); - at least one means of valorizing (640;900;910) at least a part of the energy of the outgoing flux (FS;FEls,FE2s,FRs;FCs) of said enclosure (602-606;802,606) or of at least one of said enclosures (602-606;802,606).

13. System (600;700;800) according to the preceding claim, characterized in that it comprises: - a single enclosure (802) in which the heating and compression of the battery (200) are carried out; - an enclosure (602), referred to as the heating enclosure, in which the heating of the battery (200) is carried out, distinct from an enclosure (604), referred to as the compression enclosure, in which the compression of the battery (200) is carried out.

14. System (600;700;800) according to any one of claims 12 or 13, characterized in that the recovery means (640;920) comprises a means (922) for removing, in particular by trapping or filtering, at least a portion of the VOCs found in the outgoing stream.

15. System (600;700;800) according to any one of claims 12 to 14, characterized in that the recovery means (640;900;910) comprises a combustion or oxidation means (902), of at least some of the VOCs found in the outgoing stream (FS;FEls,FE2s,FRs;FCs).

16. System (600;700;800) according to any one of claims 12 to 15, characterized in that the recovery means (910) includes a means (912) for storing at least a part of the heat from the outgoing stream (FS;FEls,FE2s,FRs;FCs), optionally after combustion of VOCs.

17. System (600;700;800) according to any one of claims 12 to 16, characterized in that the enhancement means (900) comprises a means (902) for heating a flow (FE;FEle,FE2e,FCe) entering an enclosure, by heat transfer between the outgoing flow (FS;FEls,FE2s,FRs;FCs) and said incoming flow (FE;FEle,FE2e,FCe).

Images