Process for recovering metals present in photovoltaic modules

Abstract

Process for recovering metals from photovoltaic modules. The process comprises the steps of: a) supplying the multilayer assembly comprising a plurality of laminated stacks, each laminated stack comprising: - a substrate containing crystalline silicon, - metallic elements, - a first encapsulation layer, - a second encapsulation layer; b) applying a hydrothermal treatment to the multilayer assembly, including placing the plurality of laminated stacks in an aqueous solution and applying heat to initiate separation between the substrate and the metallic elements; c) applying an ultrasonic treatment to finalize the separation between the substrate and the metallic elements and recover the metallic elements. Figure for the abbreviation: Figure 1

Description

Title of the invention: Method for recovering metals present in photovoltaic modules

[0001] The present invention relates to the field of photovoltaic module recycling and, in particular, to the recovery of metals contained in a module. Specifically, the invention concerns a two-in-one process for recovering and separating the metals used in photovoltaic modules for recycling.

[0002] To date, the European Directive 2012 / 19 / EU on Waste Equipment Waste Electrical and Electronic Equipment (WEEE) regulations mandate that manufacturers achieve an 85% mass recovery rate for materials used in photovoltaic modules, with 80% of this mass being reused or recycled. Since the module's weight is primarily due to the weight of the glass used (71.9%), recycling efforts have largely focused on delamination processes for the glass plate protecting the module's front face. However, this glass represents only 8% of the total economic value of all materials used. Metals, and particularly the metals in the photovoltaic cells, represent only a small portion of the total weight of photovoltaic panels, but their economic contribution can reach 66% of the raw material cost.Therefore, and given their scarcity and the need for strategic metals in France and Europe, it is worthwhile to examine the problem of finding an environmentally friendly technology that would allow the recovery of various metals.

[0003] Existing known processes allow for the separation of metals from a photovoltaic module frame that has undergone a manual or mechanical disassembly step and a critical glass delamination step by thermal, mechanical, or chemical means, resulting in the removal and loss of the plastic encapsulant. Furthermore, this separation uses powerful and toxic reagents, requiring organic solvents and therefore costly treatment of toxic effluents. This significantly impacts the financial benefit of recycling. In the case of a crushing process followed by physical separation, the metal selectivity is not optimal, and the recovered glass is contaminated by various dust particles from other materials.

[0004] A particular module recycling method described in EP3118902 proposes an oxidative treatment under subcritical conditions allowing the separation of the glass from the rest of the module. This method recommends the use of a highly concentrated oxidizing reagent such as HNO3 and / or H2O2 at a concentration of 30 to 65% by weight, at a temperature between 130 and 150°C, for a duration of 3 to 6 hours. autogenous pressure between 0.5 and 2.5 MPa. However, this cycle time is very long, the chemical reagents are dangerous and degrade the encapsulant which cannot be reprocessed.

[0005] Another method described in document WO2020 / 240126 uses a milder chemical process to directly recover Ag bars from end-of-life cells or production scrap. It uses etching steps in acidic and basic media with or without the application of ultrasound between 40 and 100 kHz and, in particular, highly toxic chemicals such as HF.

[0006] Thus, the present invention aims to overcome the drawbacks mentioned above. To this end, the invention proposes a method for recovering at least one metal present on a multilayer assembly, the multilayer assembly comprising, in particular, interconnected photovoltaic cells, the recovery method comprising the following steps:

[0007] a) supplying the multilayer assembly comprising a plurality of laminated stacks, each of the laminated stacks comprising:

[0008] - a support comprising at least crystalline silicon,

[0009] - metallic elements attached to the support, the metallic elements being chosen particularly in the group consisting of copper, silver and aluminum,

[0010] - a first encapsulation layer laminated on at least one front face of the support, and

[0011] - a second encapsulation layer laminated on at least one rear face of the support,

[0012] b) application of a hydrothermal treatment to the multilayer assembly comprising placing the plurality of laminated stacks in an aqueous solution to form an aqueous suspension and applying heat to degrade the first and second encapsulation layers, release the support and initiate separation between the support and the metallic elements,

[0013] c) application of an ultrasonic treatment so as to finalize the separation between the support and the metallic elements forming a suspension of residual solids and recover the metallic elements.

[0014] The inventors have thus developed a process for separating the metals from the rest of the structure under mild conditions to release the support from the first and second encapsulation layers and to detach the metals present on the support. This two-in-one process is green in that it does not use toxic and environmentally hazardous solvents. This is particularly innovative because these solvents are commonly used to remove polymers from encapsulation layers. Hydrothermal treatment in an aqueous medium, at temperature and under autogenous pressure, advantageously allows The polymers are degraded and solubilized in the aqueous phase, allowing for their subsequent recovery while simultaneously releasing the substrate. In one variation, pressure can be applied and controlled. The detachment of metallic elements is also initiated at this stage, and then ultrasonic treatment, while generating fragmentation of the multiple laminated stacks, finalizes the separation between the metallic elements and the silicon substrate. A suspension of residual solids, comprising a mixture of water-separable elements, is then obtained. Simple filtration of the solids, followed by a mechanical recovery step such as particle size sorting or density sorting, allows for the separation of the silicon fragments from the metals. This facilitates their subsequent purification and minimizes the use of acidic solutions, which are typically used for metal separation.

[0015] In this document, the term 'heating' refers to a "temperature increase" in the reactor. This can be gradual, resulting in subcritical conditions with minimal autogenous pressure. It can also be more intense, with a correspondingly higher pressure, generating supercritical conditions. However, this heating is quite different from that of a delamination heat treatment, whether by pyrolysis or incineration. While subcritical conditions offer significant energy savings compared to pyrolysis, supercritical conditions, although more drastic, remain a more economical option than pyrolysis.

[0016] According to one provision, the hydrothermal treatment of step b) is carried out in a sealed hydrothermal treatment autoclave to obtain autogenous pressure and achieve subcritical or supercritical conditions.

[0017] The autogenic pressure is determined by the temperature and the volume of water introduced into the autoclave.

[0018] According to one possibility, the pressure is controlled by means of mechanical regulating equipment.

[0019] According to one provision, step c) is carried out concomitantly with step b), for example step c) is carried out during the cooling of the aqueous suspension formed in step b).

[0020] According to one embodiment, step c) is carried out at the same time as the cooling of the aqueous suspension formed in step b).

[0021] According to one possibility, step c) is carried out after step b), in particular the aqueous suspension obtained at the end of step b) is moved into an auxiliary ultrasonic device in order to carry out step c).

[0022] According to one provision, the process further comprises a step d) carried out after step c) comprising filtration and drying of the residual solids, in order to implementation of a physical separation process for residual solids, such as particle size sorting or density sorting.

[0023] According to one possibility, the hydrothermal treatment according to step b) and / or the ultrasonic treatment according to step c) is repeated several times, in particular repeated once under conditions independent of the initial conditions.

[0024] According to one provision, the hydrothermal treatment according to step b) further includes the addition of an oxidizing agent to the aqueous suspension, in particular a hydrogen peroxide solution H2O2, so as to obtain a mass concentration of between 0 and 20% by weight of H2O2 in the aqueous solution, preferably between 0.1% and 17% by weight, and in particular between 1 and 15% by weight in the aqueous solution.

[0025] According to one possibility, the concentration of the laminated stacks in step b) is between 1g of residual solid for 30g of aqueous solution and 1g of residual solid for 5g of aqueous solution, and for example a concentration of 1g of residual solid for 18g of aqueous solution, 1g of residual solid for 20g of aqueous solution, or even 1g of residual solid for 23g of aqueous solution.

[0026] According to one provision, the hydrothermal treatment according to step b) is carried out by applying a heating of between 50°C and 400°C for 30 min to 4h, preferably by applying a heating of between 150 and 250°C for 1h30 and 2h30 so as to reach an autogenous pressure of about 20 bars (subcritical conditions) or by applying a heating of between 350°C and 420°C for 1h30 to 2h30 so as to reach an autogenous pressure of about 290 bars (supercritical conditions).

[0027] According to one possibility, the ultrasonic treatment according to step c) includes the application of waves with a frequency between 20 and 80 kHz, for example between 30 and 40 kHz and in particular at 37 kHz, in particular at atmospheric pressure, and in particular over a period of between 15 min and 70 min, for example between 20 and 60 min.

[0028] According to one provision, the process includes before step a) a step i) comprising a delamination of a possible glass plate laminated on the front face of the multilayer assembly and / or of a possible sheet of plastic material on the back face (or backsheet), in particular when the multilayer assembly includes photovoltaic cells.

[0029] According to a particular embodiment of step i), delamination is carried out according to the procedure described in document WO2020 / 104754.

[0030] According to one arrangement, the material of the first encapsulation layer and the material of the second encapsulation layer are chosen independently of each other from among polymers, and in particular from the group consisting of poly(ethylene- vinyl coacetate (or EVA), polyolefin elastomer (POE), ionomer, poly(vinyl butyral) (PVB), poly(dimethylsiloxane) (PDMS), and thermoplastic polyurethane (TPU). These polymers are advantageously capable of partially or even completely degrading under hydrothermal conditions, that is, in water heated to high temperature and high pressure (subcritical or supercritical conditions), with or in the absence of an oxidant.

[0031] According to one possibility, the plurality of rolled stacks is subjected to a dimension reduction step before the application of the hydrothermal treatment according to step b). This may be useful depending on the volume of the hydrothermal reactor used. When the rolled stacks are not reduced in size, the hydrothermal treatment may require a longer duration.

[0032] According to other features, the recovery method of the invention comprises one or more of the following optional features considered alone or in combination: - The hydrothermal treatment autoclave is a sealed reactor designed to withstand high temperatures and high pressures. - The plurality of laminated stacks includes photovoltaic cells. - The photovoltaic cells are interconnected or not. - The photovoltaic cell is chosen from the group consisting of Al-BSF (Aluminum Back Surface Field), PERC (Passivated Emitter and Rear Contact), PERL (Passivated Emitter with Rear Centrally Diffused), PERT (Passivated Emitter with Rear Totally Diffused), TOPCon (Tunnel Oxide Passivated Contact), IBC (Interdigitated Back Contact) type cells and heterojunction cells. - The process is applied to a mixture of different types of photovoltaic cells at the same time. - Photovoltaic cells can be manufacturing waste, with or without interconnections, or be found within the laminated stack. - The support includes at least one silicon wafer, n-doped, p-doped or intrinsically undoped. - A silicon wafer is a self-supporting layer of silicon with a thickness of at least 100 micrometers. - The support also includes a plurality of layers bonded to the silicon wafer, including passivation layers, antireflective layers, emitting layers, tunnel junctions, for example in silicon nitride, silicon oxide, Al2O3, TCO (Transparent Conductive Oxide) layers. - The substrate is mostly made of crystalline silicon. - Silicon is monocrystalline - Silicon is polycrystalline. - The first encapsulation layer covers the entire front face of the support. - The second encapsulation layer covers the entire back face of the support. - The front face of the support is the face intended to receive the sun's rays. - The back face of the support is the face opposite the front face. - The metallic elements are intended for the conduction of electric current. - The metallic elements include electrical current collectors on the front and / or rear face of the support, including current collectors made of Ag and Al, and Cu or Cu / Ag interconnection bars linking the photovoltaic cells together. - The aqueous suspension obtained at the end of step b) is filtered and the recovered solids are washed, then dried in an oven at 50°C, then the solids are resuspended in water before carrying out step c). - The ultrasonic treatment of step c) is carried out in situ, i.e. directly in the autoclave housing a sonotrode device, so as to limit intermediate or transfer steps. - The initial conditions are the conditions for carrying out the first hydrothermal treatment according to step b) of the process and / or ultrasonic treatment according to step c) of the process. - The ultrasonic treatment according to step c) is carried out over a temperature range between 20 and 50°C.

[0033] Other aspects, objectives and advantages of the present invention will become more apparent from the following description of an embodiment thereof, given by way of non-limiting example and with reference to the following figures:

[0034] [Fig. 1] is a schematic view representing a laminated stack from an Al-BSF type Si-based photovoltaic panel according to an embodiment of the invention.

[0035] [Fig.2] is a view illustrating a photograph of PERC-type cell fragments according to the invention and SEM images illustrating the metallic elements on the Si support.

[0036] [Fig.3] is a view illustrating photographs of stack fragments and a snapshot SEM illustrating the metallic elements separated from the Si support according to an embodiment of the invention.

[0037] [Fig.4] is a view of a SEM image illustrating the front surface of the support of silicon after application of hydrothermal treatment according to an embodiment of the invention.

[0038] [Fig.5] is a view of a SEM image illustrating the rear surface of the support of silicon after application of hydrothermal treatment according to an embodiment of the invention.

[0039] [Fig.6] is a view of a SEM image illustrating the front surface of the silicon support after application of the process according to an embodiment of the invention.

[0040] [Fig.7] is a view of a SEM image illustrating the rear surface of the support of silicon after application of the process according to an embodiment of the invention.

[0041] The inventors first implemented the process for recovering metals (front-side collectors 1 in Ag, rear-side collectors in Al 2, interconnections 3 in Cu) present on an assembly of multilayers 100, in particular a crystalline silicon-based photovoltaic cell containing no encapsulation layer 5 ([Fig. 1]). This type of cell 100' comes, for example, from manufacturing scrap or from an assembly of multilayers 100' from which the glass plate V, the backsheet 4, and the encapsulation layers 5 have been previously removed.

[0042] In particular, the inventors considered 100' PERC-type photovoltaic cells without glass, a backsheet 4, or an encapsulation layer 5, as illustrated in [Fig. 1]. Fragments of the 100' photovoltaic cell before processing are shown in [Fig. 2] as a reference. The enlarged regions in the SEM images clearly illustrate the Ag collectors 1 on the front face of the Si support 6, as well as the Al collector 2 on the rear face (resembling a sintered area).

[0043] The procedure followed comprises the following steps:

[0044] 0.5 g of 100' photovoltaic cell is introduced into a 45 mL autoclave (Parr, no. 4744) (step a) with a hydrogen peroxide (H2O2) solution of mass concentration that was varied between 0 and 15 wt% (step b) depending on the experiments. These were carried out with a mass ratio of aqueous solution varying from 1 g cell / 9 g of solution to 1 g cell / 26 g of solution.

[0045] The autoclave is placed in an oven for treatment under mild subcritical conditions, namely an operating temperature of 200 or 230°C for 2 hours (the pressure is self-generated and determined by the amount of water in the autoclave). At the end of the experiment, the entire assembly is cooled to room temperature and the aqueous suspension (i.e., treated 100' photovoltaic cells and aqueous solution) is transferred to an ultrasonic device which is closed before being subjected to ultrasonic treatment at approximately 37 kHz (step c) for approximately 60 min.

[0046] At the end of the ultrasonic (US) treatment, the suspension is filtered through a PTFE filter having a pore size of 0.45 µm and the recovered solids are dried in an oven at 50°C ([Fig. 3]). The separated 100' cell fragments are then sieved at 500 µm to obtain, on the one hand, a silicon-rich fraction (particles approximately > 500 µm) and, on the other hand, a silver- and aluminum-rich fraction (particles approximately < 500 µm). Indeed, observation of all the 100' cell fragments obtained after ultrasonic treatment makes it very easy to distinguish that the silicon support fragments 6 are quite large (fractions > 500 µm) and that the silver and aluminum particles 7 are much smaller (fractions < 500 µm). Sieving at 500 µm is therefore chosen in order to obtain two types of metallic fractions: the first, rich in silicon, i.e., those larger than 500 µm; and the second, rich in silver and aluminum, i.e., those smaller than 500 µm (SEM image of [Fig. 3]). This choice is entirely arbitrary and serves primarily analytical purposes.

[0047] Chemical analyses by ICP-AES make it possible to quantify the metals in each fraction.

[0048] The results of the recovery of the 1,2 separate metals are recorded in Table 1 below. The percentage of detachment of the metallic elements (Ag and Al) from the substrate (Si) is calculated using the following formula (I):

[0049] [Math.l] - mass cHFuie > SQOpm s® « s se ce 1 sj « ic ? « ; ts « 1 e x 100 (I)

[0050] For comparison purposes, additional tests were carried out on 100' cell fragments not treated by hydrothermal treatment (HT) and having only undergone ultrasonic treatment (US), so as to serve as a reference control (input 1) to evaluate the effectiveness of the hydrothermal treatment.

[0051] [Tab 1] Mass concentration of H2O2 at the HT inlet (°C) US (kHz) Cell concentration in g / s Solution in g 0% 1% 5% 10% 15% 1 -na- 37 1 / 26 4.0 3.2 1.3 1.8 3.8 2 200 37 1 / 9 2.9 7.2 7.2 7.0 7.1 3 200 37 1 / 18 7.3 7.9 7.1 7.1 7.4 4 200 37 1 / 26 7.5 6.8 7.1 7.4 7.0 5 230 37 1 / 26 8.1 6.9 7.5 7.6 7.0

[0052] Table 1: Metal detachment from the cell (in %) - Maximum theoretical detachment of 7.8%. If the measured detachment is greater than the theoretical value, this may be due to a sampling bias.

[0053] Entry 1 of Table 1 shows the importance of carrying out the hydrothermal treatment before applying the ultrasound treatment. Indeed, without HT treatment, the observed debonding percentage is limited to 4%, whereas with HT treatment (under subcritical conditions - pressure between 15 and 50 bar), it is possible to obtain debonding of all the metals 1,2. It can also be noted that the lower the mass concentration of solid in the solution (higher dilution), the better the debonding results. This can be counterbalanced by the presence of the oxidizing agent H2O2, which, at 1%, leads to similar results for a dilution half as large (refer to entries 2 and 3, the same debonding obtained for a concentration 1:9 with 1 wt% H2O2 instead of a concentration 1:18 without H2O2).

[0054] Thus, performing the hydrothermal treatment before the ultrasound greatly facilitates the detachment of the silver collectors 1 (front face) and aluminum collectors 2 (rear face) from the silicon support 6. Variations in the mass concentration of H2O2, the cell-to-solution mass ratio, and the temperature have little impact on the detachment.

[0055] This is corroborated by Figures 2 and 3, illustrating photographs and SEM images respectively before and after implementation of the process of the invention. Before treatment, silver collectors 1 can be observed on the front face and aluminum collectors 2 on the rear face of the debris from a PERC cell. After both treatments, the cell debris shows the absence of silver and aluminum collectors 1 and 2. The SEM image also shows a magnification of the Ag- and Al-rich solid fraction (size less than 500 micrometers) where silver bar residues (very light color) and Al elements (darker color) can be distinguished.

[0056] Furthermore, the importance of the US treatment is clearly demonstrated by the SEM images in Figures 4 and 5, which illustrate the partial detachment of the collectors 1,2 after HT treatment and before US treatment. In [Fig. 4], the image shows the beginning of the detachment of the Ag collectors 1 on the front face of the support 6. In [Fig. 5], the image shows the detachment of most of the aluminum collectors 2 on the rear face of the support 6. Thus, the US treatment is very useful for completing the detachments of the metals 1,2 observed in the solid residues ([Fig. 3]).

[0057] After hydrothermal and ultrasonic treatment, the metallic particles 7 are roughly separated by sieving at 500 micrometers in order to obtain a A silicon-rich fraction and another fraction rich in aluminum and silver are separated. Each fraction is then completely dissolved and chemically characterized. The results show that the silicon purity of the silicon-rich fraction is, in some cases, greater than 99% (metallurgical-grade silicon) when using water alone. The addition of an oxidant, such as H₂O₂, in relatively low concentrations, less than 15% by mass, allows for similar or even higher purities, even with higher cell concentrations.

[0058] Chemical analysis of the silver and aluminum-rich fraction (less than 500 micrometers) shows that the use of water under certain operating conditions, namely a temperature of 230°C and a cell mass ratio of 1g:26g, makes it possible to recover in solid form all of the aluminum and more than 90% of the silver mass contained in the 100' photovoltaic cell. The addition of an oxidant, such as H2O2 in mass concentrations in water between 1 and 15% by weight, makes it possible to reduce the operating temperature of the hydrothermal treatment and to increase the concentration of 100' photovoltaic cells in the water.

[0059] The inventors then determined the optimal conditions for degrading the most commonly used material for forming the encapsulation layers 5 in photovoltaic modules, namely EVA. It can be present as a solid layer on the cell support 6 or in foamed form, for example, when the pre-delamination of the glass plate V of the photovoltaic module is carried out by reaction with CO2 under supercritical conditions. A complete description of the reaction with CO2 is given in document WO2020 / 104754. The inventors evaluated the degradation of these two types of EVA: foamed by CO2 and unfoamed.

[0060] Examples of implementation of the degradation of non-foamed EVA by the hydrothermal treatment of step b) are carried out as follows:

[0061] A sheet of EVA (Lushan EV1050G1 / RF) is first laminated between two Teflon plates to activate the crosslinking agents and then cut into pieces approximately 1 to 2 cm square. 0.2 g of EVA (average surface area of ​​1.18 cm²) is then placed in a 45 mL autoclave (Parr, no. 4744). A mixture of water and hydrogen peroxide (H₂O₂) with a mass concentration of H₂O₂ between 0 and 15% by weight is added to the sample at a mass ratio of 1 g EVA:solution:23 g. The autoclave is then placed in an oven and heated to a temperature between 180 and 220°C, preferably 200°C, for 2 to 4 hours, preferably 2 hours. The pressure in the autoclave is self-sustaining. The tests are carried out in triplicate. The percentage of degradation is defined according to the following formula (II):

[0062] [Math.2] nwreftHtMte - mass i'tMaîe f 2 =........................... '...........'■■■ >: 106 1 ' ' mass wttu« (II)

[0063] Table 2 below records the results obtained according to the treatment conditions.

[0064] [Tab 2] Mass concentration of H2O2 Inlet HT (°C) Duration in hours 0% 1% 5% 10% 15% 1 180 2 1.40 5.59 15.07 13.52 14.19 2 200 2 4.24 14.82 57.01 80.43 83.53 3 220 2 4.63 14.44 53.40 62.89 74.74 4 200 4 4.22 13.53 50.55 69.68 78.83 5* 200 2 39.8 63.1 79.6

[0065] Table 2: Degradation of TEVA by HT treatment. * EVA foamed by CO2 treatment

[0066] The best result is obtained with a high-temperature (HT) treatment at 200°C for 2 hours in the presence of 15% by weight of H2O2 oxidant (input 2). Input 5 illustrates the results of the test carried out on an EVA sample that had undergone a preliminary foaming step under conditions identical to those used for the delamination of the glass plate V of the photovoltaic module. The sample considered comprises a solid layer of EVA laminated between two Teflon plates and then foamed by a CO2 treatment under supercritical conditions (130 bar, 75°C, 30 min). The HT treatment applied is identical to that applied to unfoamed EVA. In conclusion, the degradation results of foamed EVA are similar to those obtained from unfoamed EVA.

[0067] The liquid phase recovered at the end of the HT treatment is analyzed by chromatography to verify the degradation of EVA. GC-MS analyses of the liquid phase initially show the deacetylation of the vinyl acetate motif, the product of which is acetic acid (a), followed by the cleavage of the residual ethylene carbon skeleton into carboxylic acids, ketones, lactones, etc.

[0068] The inventors then implemented the process of the invention on a set of multilayers 100. To do this, they considered an EVA / cell 100' / EVA sandwich, having previously undergone a delamination step by CO2 under supercritical conditions (75°C, 2 cycles, 130 bars / 30 min, 150 bars / 10 min) in order to remove the glass plate V and the backsheet 4 from the module and which led to the foaming of the EVA. The EVA used is Lushan EV1050G1 / RF ® and the 100' cells are PERC type, non-interconnected.

[0069] Approximately 10g of this sandwich are placed in a 600mL autoclave. Then, 180mL of an 85:15 water:H2O2 solution by weight is added. The autoclave is then closed and heated to a set temperature of 200°C (autogenous pressure of approximately 50 bar) for 4 hours (not including a 30-minute heating period and a 30-minute cooling period with compressed air to ambient temperature). A first perforated basket with a stainless steel filter (REPS mesh, 25µm) at the bottom serves as a receptacle for the by-products of the EVA hydrolysis. The samples to be treated are placed in a second perforated basket, positioned above the first, with a stainless steel filter (square mesh, 220µm) allowing the collection of the 100' photovoltaic cell fragments released during the HT treatment. Once processed, the solid and liquid are separated. The residual solid sample (i.e.The cell, residual EVA and by-products) is dried and then separated to recover the released cell fraction, which is then rinsed and dried again in an oven at 50°C. This fraction is placed in a flask under water and then placed in an ultrasonic bath (37kHz) for 1 hour. A solid-liquid separation is carried out by filtration through 0.45 micrometer PTFE and the residual solid is dried in an oven at 50°C.

[0070] The analyses performed show that 31.1% of EVA was degraded and that 2.2% of the cell was released. The following formulas III and IV were used respectively to perform these calculations:

[0071] [Math.3] Mass ««■Mdwù'h swiMsfs? — m«s.se saMdutoY fbuste =---------------------------------------TïTTr-;---------™-----------rv;--------~-------------X 1S6 (IV)

[0072] [Math.4] <k-=............................................................................................... 100 ' (Bass ete eeUïB'e «tans êe (V)

[0073] In light of this result, the process of the invention was implemented again under supercritical conditions. Approximately 10g of the CO2-treated sandwich, under the same conditions as before, are placed in a closed (airtight) autoclave and heated to 400°C (autogenous pressure of 288 bar) for 2 hours (not including an 80-minute heating period and a 30-minute cooling period with compressed air to ambient temperature). A first perforated basket with a stainless steel filter (25µm REPS mesh) at the bottom serves as a receptacle for the by-products of the EVA hydrolysis. The samples to be treated are placed in a second basket. A perforated chamber, positioned above the first, is fitted with a stainless steel filter (square mesh, 220 µm) to collect the 100' photovoltaic cell fragments released during processing. Once processed, the solid and liquid are collected separately. Complete detachment of the Ag collectors (1) is observed, as their particles (7) have dissolved in the aqueous suspension ([Fig. 6]). The Ag then precipitates onto the reactor walls during cooling and can be recovered by acid treatment, for example, by adding nitric acid. The residual solid sample (i.e., cell, residual EVA, and degradation byproducts) is dried and then separated to recover the released 100' cell fraction, which is rinsed and dried again in an oven at 50°C. This fraction is placed in a water-filled flask and then immersed in an ultrasonic bath (37 kHz) for 1 hour. The suspension is filtered and then dried in an oven at 50°C before sieving at 500qm.Analyses show that 49.1% of the EVA was degraded and that the cell was 100% freed by the HT treatment under supercritical conditions. The US treatment partially detached the aluminum collectors 2 (refer to [Fig. 7]). A second, repeated US treatment on the support 6 containing aluminum completed the separation of the aluminum collectors 2. Silver.

[0074] According to an unillustrated provision, it is possible to repeat the entire process (treatments of steps b and c) under the same conditions as before or under milder conditions in order to separate all of the metallic elements 1,2.

[0075] According to another, unrepresented, embodiment, the invention is implemented with the copper interconnectors 3 on the cells 100'. Since the copper interconnectors 3, or bars, are simply soldered to the front and rear collectors 1,2, the interconnectors 3 remain attached to the collectors 1,2 when these collectors 1,2 are separated from the support 6, or they can be separated from the collectors 1,2. Thus, the copper interconnectors 3 are recovered in the separable suspension. They are then isolated during the physical separation processes of the residual solids.

[0076] Thus, the present invention makes it possible to delaminate the encapsulation layers 5 and detach metals 1, 2, 3 from photovoltaic cells 100' without the use of solvents and with a lower environmental impact and energy cost than the processes used to date. The process allows the recovery of metals 1, 2, notably in solid form, suspended in water, which facilitates their separation and purification while minimizing the use of conventional acidic reagents. Furthermore, step b) of the HT treatment can be carried out in batch mode or in semi-dynamic mode with decorrelation of temperature and pressure, which offers interesting modularity for integration into industrial processes.

Claims

Demands

1. A method for recovering at least one metal present on a multilayer assembly (100), the multilayer assembly (100) comprising in particular interconnected photovoltaic cells (100'), the recovery method comprising the following steps of: a) supplying the multilayer assembly (100) comprising a plurality of laminated stacks, each of the laminated stacks comprising: - a support (6) comprising at least crystalline silicon, - metallic elements (1, 2, 3) bonded to the support (6), the metallic elements (1, 2, 3) being selected in particular from the group consisting of copper, silver and aluminum, - a first encapsulation layer (5) laminated on at least one front face of the support (6), and - a second encapsulation layer (5') laminated on at least one rear face of the support (6),b) application of a hydrothermal treatment to the multilayer assembly (100) comprising placing the plurality of laminated stacks (100') in an aqueous solution to form an aqueous suspension and applying heat to degrade the first and second encapsulation layers (5, 5'), release the support (6) and initiate separation between the support (6) and the metallic elements (1, 2, 3), c) application of an ultrasonic treatment to finalize the separation between the support (6) and the metallic elements (1, 2, 3) forming a suspension of residual solids and recovering the metallic elements (1, 2, 3).

2. A method for recovering at least one metal according to claim 1, wherein step b) is carried out in a sealed hydrothermal treatment autoclave to obtain autogenous pressure and achieve subcritical or supercritical conditions.

3. A method for recovering at least one metal according to claim 1 or 2, wherein step c) is carried out concomitantly with step b), for example step c) is carried out during the cooling of the aqueous suspension formed in step b).

4. A method for recovering at least one metal according to claim 1 or 2, wherein step c) is carried out after step b), in particular the aqueous suspension obtained at the end of step b) is moved into an auxiliary ultrasonic device in order to carry out step c).

5. A method for recovering at least one metal according to any one of claims 1 to 4, comprising a step d) carried out after step c) comprising filtration and drying of the residual solids, for the purpose of carrying out a physical separation process of the residual solids, such as particle size sorting or density sorting.

6. A method for recovering at least one metal according to any one of claims 1 to 5, wherein the hydrothermal treatment according to step b) and / or the ultrasonic treatment according to step c) is repeated several times, in particular repeated once under conditions independent of the initial conditions.

7. A method for recovering at least one metal according to any one of claims 1 to 6, wherein the hydrothermal treatment according to step b) further comprises the addition of an oxidizing agent to the aqueous suspension, in particular a hydrogen peroxide solution H2O2, so as to obtain a mass concentration of between 0 and 20% by weight of H2O2 in the aqueous solution, preferably between 0.1% and 17% by weight, and in particular between 1 and 15% by weight in the aqueous solution.

8. A method for recovering at least one metal according to any one of claims 1 to 7, wherein the concentration of the stacks rolled in step b) is between 1g of residual solid per 26g of aqueous solution and 1g of residual solid per 9g of aqueous solution, and for example a concentration of 1g of residual solid per 18g of aqueous solution, 1g of residual solid per 20g of aqueous solution, or even 1g of residual solid per 23g of aqueous solution.

9. A method for recovering at least one metal according to any one of claims 1 to 8, wherein the hydrothermal treatment according to step b) is carried out by applying heat from between 50°C and 400°C for 30 min to 4 h, preferably by applying heat from between 150 and 250°C for 1.5 to 2.5 h so as to reach an autogenous pressure of about 20 bar, or by application of heating between 350°C and 420°C for 1h30 to 2h30 so as to reach an autogenous pressure of approximately 290 bars.

10. A method for recovering at least one metal according to any one of claims 1 to 9, wherein the ultrasonic treatment according to step c) comprises the application of waves of frequency between 20 and 80 kHz, for example between 30 and 40 kHz and in particular at 37 kHz, in particular at atmospheric pressure, and in particular for a period of between 15 min and 70 min, for example between 20 and 60 min.

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