Electrochemical recycling of lead-based materials

Abstract

The present application relates to the electrochemical extraction of lead (Pb) from a lead-containing material using a deep eutectic solvent. This is of particular use in the recycling of the lead-based materials that result from energy generation processes.

Claims

1. A method for extracting lead from a lead-based material, the method comprising: dissolving the lead-based material in a deep eutectic solvent to form an electrolyte; providing a working lead electrode in electrical contact with the electrolyte; providing a counter electrode in electrical contact with the electrolyte; and generating a potential through the electrolyte, thereby reducing a lead species of the lead-based material in the electrolyte at the working lead electrode, so as to deposit the reduced lead species as deposited, reduced lead metal onto the working lead electrode; wherein the lead-based material is from a lead acid battery, a lead perovskite photovoltaic and/or lead thermoelectric and comprises PbO.sub.2, PbSO.sub.4, CH.sub.3NH.sub.3PbHaI.sub.3, HC(NH.sub.2).sub.2PbHaI.sub.3, CH.sub.3NH.sub.3PbI.sub.3-XCl.sub.X or PbTe, or a mixture thereof, wherein HaI is I, Cl, or Br, and X is a value between 0 and 3; and wherein the deposited, reduced lead metal and the working lead electrode is suitable for direct recycling or reusing as one piece, without need for further processing to separate the lead from the electrode.

2. The method of claim 1, wherein the deep eutectic solvent comprises a hydrogen bond donor and a quaternary ammonium salt.

3. The method of claim 1, wherein the potential applied is equal to, or more negative than, the Pb(II) to Pb reduction potential.

4. The method of claim 1, wherein the deep eutectic solvent is maintained at a temperature above about 20 C.

5. The method of claim 1, wherein the method further comprises: dissolving the lead-based material in a deep eutectic solvent to form the electrolyte; providing a working electrode in electrical contact with the electrolyte; providing a counter electrode in electrical contact with the electrolyte; generating a potential through the electrolyte, thereby reducing the lead species of the lead-based material in the electrolyte at the working electrode so as to deposit the reduced lead species on the working electrode as lead metal; and collecting the deposited lead metal.

6. The method of claim 1, wherein the counter electrode is an IrO.sub.2-coated Ti electrode.

7. The method of claim 1, wherein the method further comprises providing a reference electrode in electrical contact with the electrolyte.

8. The method of claim 1, wherein the lead-based material is dissolved in the deep eutectic solvent at a temperature above about 20 C. to form the electrolyte.

9. An electrochemical cell capable of reducing a lead species in a lead-based material so that the reduced lead species is deposited at a working electrode, the cell comprising: an electrolyte comprising a solution of the lead-based material dissolved in a deep eutectic solvent; a working lead electrode in electrical contact with the electrolyte; and a counter electrode in electrical contact with the electrolyte; wherein the lead-based material is from a lead acid battery, a lead perovskite photovoltaic and/or lead thermoelectric and comprises PbO.sub.2, PbSO.sub.4, CH.sub.3NH.sub.3PbHaI.sub.3, HC(NH.sub.2).sub.2PbHaI.sub.3, CH.sub.3NH.sub.3PbI.sub.3-XCl.sub.X or PbTe, or a mixture thereof, wherein HaI is I, Cl, or Br, and X is a value between 0 and 3; wherein the reduced lead species is deposited on the working lead electrode; and wherein the deposited reduced lead metal adhered to the working lead electrode is suitable for direct recycling or reusing as one piece, without need for further processing to separate the lead from the electrode.

10. The electrochemical cell of claim 9, wherein the counter electrode is an IrO.sub.2-coated Ti electrode.

11. The electrochemical cell of claim 9 comprising a reference electrode in electrical contact with the electrolyte.

12. The electrochemical cell of claim 9, wherein the deep eutectic solvent comprises a hydrogen bond donor and a quaternary ammonium salt.

13. The electrochemical cell of claim 9, wherein the electrolyte is maintained a temperature above about 20 C.

14. The electrochemical cell of claim 9, wherein the lead-based material is dissolved in the deep eutectic solvent at a temperature above about 20 C. to form the electrolyte.

15. A method for extracting lead from a lead-based material, the method comprising: dissolving the lead-based material from a lead acid battery, a lead perovskite photovoltaic and/or lead thermoelectric in a deep eutectic solvent to form an electrolyte; providing a working lead electrode in electrical contact with the electrolyte; providing a counter electrode in electrical contact with the electrolyte; and generating a potential through the electrolyte, thereby reducing a lead species of the lead-based material in the electrolyte at the working electrode so as to deposit the reduced lead species as lead metal; and wherein the deposited reduced lead metal and the working electrode is suitable for direct recycling or reusing as one piece, without need for further processing to separate the lead from the electrode.

16. The method of claim 2, wherein the hydrogen bond donor is ethylene glycol or urea and the quaternary ammonium salt is choline chloride, and wherein the ethylene glycol:choline chloride, or urea:choline chloride are present in a molar ratio of 2:1.

17. The method of claim 1, wherein the reference electrode is an Ag-wire quasi-reference electrode.

18. The electrochemical cell of claim 11, wherein the reference electrode is an Ag-wire quasi-reference electrode.

19. The electrochemical cell of claim 12, wherein the hydrogen bond donor is ethylene glycol or urea and the quaternary ammonium salt is choline chloride, and wherein the ethylene glycol:choline chloride, or urea:choline chloride are present in a molar ratio of 2:1.

Description

DESCRIPTION OF FIGURES

(1) FIG. 1 shows a cyclic voltammogram (CV) of an indium tin oxide (ITO) working electrode in a PbSO.sub.4 DES. The reduction peak R is attributed to Pb(II) to Pb reduction and deposition on the ITO, whilst O is an oxidative stripping processes.

(2) FIG. 2 shows x-ray diffraction (XRD) patterns of Pb deposited on an ITO working electrode from a PbSO.sub.4 DES for (a) 1 minute, (b) 10 minutes, (c) 30 minutes and (d) 60 minutes. The diffraction peaks demonstrate that the Pb is extracted as metallic Pb.

(3) FIG. 3 shows scanning electron microscope (SEM) images of Pb deposited on an ITO working electrode from a PbSO.sub.4 DES for (a) 1 minute, (b) 10 minutes, (c) 30 minutes and (d) 60 minutes. The large white particles are attributed to being Pb.

(4) FIG. 4 shows SEM images of the Pb foil working electrode (a) following 120 hours of Pb deposition, (b) following 1 hour of Pb deposition, (c) following 120 hours of control deposition from a DES with no PbSO.sub.4, (d) polished Pb foil prior to deposition.

(5) FIG. 5 shows XRD patterns of Pb foil (a) following 120 hours of Pb deposition from the PbSO.sub.4 DES, (b) 1 hour of Pb deposition from the PbSO.sub.4 DES, (c) 120 hours of Pb-less deposition from the control DES and (d) the polished Pb foil pre-deposition.

(6) FIG. 6 shows a CV of an ITO working electrode in the PbO.sub.2 DES. The reduction peak at which Pb is deposited is labelled R, whilst the oxidative stripping peak is labelled O.

(7) FIG. 7 shows a XRD pattern of Pb deposited potentiostatically from the PbO.sub.2 DES. The peaks labelled as In.sub.2O.sub.3 are from the ITO substrate.

(8) FIG. 8 shows a SEM image of Pb deposited potentiostatically from the PbO.sub.2 DES.

(9) FIG. 9 shows (a) CVs of an ITO working electrode in the MAPbI.sub.3, FAPbI.sub.3 and CH.sub.3NH.sub.3PbI.sub.3-XCl.sub.X DESs, as well as a control DES containing no lead perovskite. (b) XRD patterns of a blank ITO substrate, and Pb deposited from the three perovskite DESs for one hour.

(10) FIG. 10 shows an SEM image of Pb deposited from the CH.sub.3NH.sub.3PbI.sub.3-XCl.sub.X DES for 60 minutes.

(11) FIG. 11 shows XRD patterns of (a) the fluorine-doped tin oxide (FTO) substrate, (b) the TiO.sub.2-coated FTO substrate, and on the FTO-TiO.sub.2 substrates the MAPbI.sub.3 film (c) before and (d) after stripping, the FAPbI.sub.3 film (e) before and (f) after stripping, and the MAPbI.sub.3-XCl.sub.X film (g) before and (h) after stripping.

(12) FIG. 12 shows SEM images of (a) TiO.sub.2-coated FTO before the deposition of lead perovskite films, (b) and (c) MAPbI.sub.3 pre- and post-stripping respectively in the DES, (d) and (e) FAPbI.sub.3 pre- and post-stripping respectively in the DES, (f) and (g) MAPbI.sub.3-XCl.sub.X pre- and post-stripping respectively in the DES.

(13) FIG. 13 shows CVs of ITO working electrodes in a PbTe DES.

(14) FIG. 14 shows SEM images of films of Pb potentiostatically deposited from 0.6 mol EG+0.3 mol ChCl+0.17 mmol PbTe for 180 minutes at (a) 2,000 and (b) 5,500 magnification.

DETAILED DESCRIPTION OF THE INVENTION

(15) It has been determined that deep eutectic solvents may be used to electrochemically recycle lead-based materials. These lead-based materials may particularly be used in or result from energy generating processes, and these waste lead-based materials may be recycled into new lead products. Recycling of lead-based materials to produce lead involves the electrochemical extraction of lead from the lead-based material. Lead is extracted in the form of lead metal and may then be subjected to further processing steps before it may be used in new products. Alternatively, the lead may be extracted in a form that avoids the need for further processing steps, so it may be directly used in new products.

(16) Extraction of lead is achieved by dissolving the lead-based material in the deep eutectic solvent, and then selectively electrodepositing the lead onto an electrode. Accordingly, in a first aspect, the invention provides a method for extracting lead from a lead-based material, the method comprising: dissolving the lead-based material in a deep eutectic solvent to form an electrolyte; providing a working electrode in electrical contact with the electrolyte; providing a counter electrode; and generating a potential through the electrolyte, thereby reducing a lead species of the lead-based material in the electrolyte at the working electrode so as to deposit the reduced lead species at lead metal; wherein the lead-based material is selected from PbO.sub.2, PbSO.sub.4, CH.sub.3NH.sub.3PbHaI.sub.3 (MAPbHaI.sub.3), HC(NH.sub.2).sub.2PbHaI.sub.3 (FAPbHaI.sub.3), CH.sub.3NH.sub.3PbI.sub.3-XCl.sub.X (MAPbI.sub.3-XCl.sub.X) or PbTe, or a mixture thereof.

(17) Use of a working lead electrode in the recycling of lead from a lead-based material allows deposited reduced lead to be collected along with the electrode, avoiding the need for additional processing steps to separate the lead from the electrode. Accordingly, in another aspect, the invention provides method for extracting lead from a lead-based material, the method comprising: dissolving the lead-based material in a deep eutectic solvent to form an electrolyte; providing a working lead electrode in electrical contact with the electrolyte; providing a counter electrode in electrical contact with the electrolyte; and generating a potential through the electrolyte, thereby reducing a lead species of the lead-based material in the electrolyte at the working electrode so as to deposit the reduced lead species as lead metal.

(18) A deep eutectic solvent (DES) is an ionic solvent that is a mixture of two or more components forming a eutectic with a melting point lower than either of the individual components. Compared to ordinary solvents, deep eutectic solvents also have a low volatility, are non-flammable, are relatively inexpensive to produce, and may be biodegradable. It has been found that deep eutectic solvents may be particularly useful in the solvation of lead-based materials and subsequent electrochemical extraction of lead from these lead-based materials.

(19) Deep eutectic solvents may be formed from a mixture of a quaternary ammonium salt (for example, choline chloride) and a hydrogen bond donor (for example, amides, alcohols or carboxylic acids). Thus, DES may be a type III DES. Particularly useful quaternary ammonium salts are quaternary ammonium halides (preferably chlorides). Quaternary ammonium salts include choline chloride (2-hydroxyethyl-trimethylammonium chloride), N-ethyl-2-hydroxy-N,N-dimethylethanaminium chloride, 2-(chlorocarbonyloxy)-N,N,N-trimethylethanaminium chloride or N-benzyl-2-hydroxy-N,N-dimethylethanaminium chloride. Particularly useful hydrogen bond donors include alcohols (such as ethylene glycol and glycerol), amides (such as urea, acetamide, 1-methyl urea, 1,3-dimethyl urea, 1,1-dimethyl urea, thiourea and benzamide), and carboxylic acids (such as malonic acid, benzoic acid, adipic acid, oxalic acid, succinic acid and citric acid), preferably a hydrogen bond donor is ethylene glycol or urea. Exemplary DES include systems formed of a mixture of an alcohol hydrogen bond donor and a quaternary ammonium salt in a 2:1 molar ratio, an amide hydrogen bond donor and a quaternary ammonium salt in a 2:1 molar ratio, or a carboxylic acid hydrogen bond donor and a quaternary ammonium salt in a 1:1 molar ratio. Preferable DES include systems formed of a mixture of ethylene glycol and choline chloride (preferably in a 2:1 molar ratio), or urea and choline chloride (preferably in a 2:1 molar ratio). Further exemplary hydrogen bond donors, quaternary ammonium salt and DES systems include those set out in E L Smith et al., Chemical Reviews, 114(21), 11060-11082, 2014, the contents of which are herein incorporated by reference.

(20) The invention concerns the extraction of lead from lead-based materials. A lead-based material of the present invention is material containing a lead compound, i.e. a material comprising lead and at least one additional element. The lead-based material may be a lead salt, in particular a lead(II) or lead(IV) salt. The lead-based materials described herein may particularly be used in or result from energy generating processes such as those carried out in batteries or solar cells or resulting from thermoelectric processes. As used herein, the term lead species relates to the lead ions of the particular lead-based material. Preferably the lead species is Pb(II) (alternative notation Pb.sup.2+), or Pb(IV) (Pb.sup.4+). Exemplary lead-based materials are compounds that contain Pb(II) or Pb(IV), such as those including the lead acid battery materials lead(II) sulfate (PbSO.sub.4), lead(IV) oxide (PbO.sub.2) and lead(II) oxide (PbO), the lead perovskite photovoltaic materials CH.sub.3NH.sub.3PbHaI.sub.3 (MAPbHaI.sub.3), HC(NH.sub.2).sub.2PbHaI.sub.3 (FAPbHaI.sub.3), CH.sub.3NH.sub.3PbI.sub.3-XCl.sub.X (MAPbI.sub.3-XCl.sub.X) and the thermoelectric material lead telluride (PbTe), or a mixture thereof, wherein HaI is I, Cl or Br preferably I, and wherein X is a value between 0 and 3, preferably X is less than 1.5, less than 1 or less than 0.5. Preferably the lead perovskite photovoltaic materials are CH.sub.3NH.sub.3PbI.sub.3 (MAPbI.sub.3), HC(NH.sub.2).sub.2PbI.sub.3 (FAPbI.sub.3) or CH.sub.3NH.sub.3PbI.sub.3-XCl.sub.X (MAPbI.sub.3-XCl.sub.X), or mixtures thereof.

(21) The lead-based materials of the invention are dissolved in the DES before electrodeposition onto an electrode. The resulting solution of the lead-based material dissolved in the DES is used as the electrolyte in the electrochemical method for lead extraction of the invention. The lead species in the electrolyte is reduced by the potential applied to form a reduced lead species. Generating a potential through the electrolyte results in production of a current flowing through the electrolyte, thereby reducing the lead species. The reduced lead species is lead metal, i.e. Pb(0). This reduced lead species is deposited on the electrode and may then be collected. The reduction of the lead species may preferably be a Pb(II) to Pb(0) reduction. Consequently, the lead species may preferably be reduced and deposited when a potential equal to, or more negative than, the Pb(II) to Pb(0) reduction potential is applied. Therefore, it is preferable to generate a potential equal to, or more negative than, the Pb(II) to Pb(0) reduction potential through the electrolyte.

(22) A working electrode is immersed in the electrolyte, so as to be in electrical conduct with the electrolyte, to form an electrochemical cell. An electrochemical cell is a device capable of facilitating chemical reactions through the introduction of electrical energy. The working electrode may apply the desired potential in a controlled way and facilitate the transfer of charge to and from the electrolyte.

(23) The lead species is reduced at the working electrode and the reduced lead may be deposited onto the working electrode. Therefore, the greater the surface area of the electrode, the greater the rate of deposition. Accordingly, it is desired to use an electrode with a high surface area proportional to its volume, for example, a foil or mesh electrode.

(24) The reduced lead may be deposited on the working electrode where it may subsequently be collected. The lead may be deposited and then delaminated from the electrode and then collected as lead separate from the electrode.

(25) The working electrode may be a metal electrode, preferably a lead electrode or an indium tin oxide (ITO) electrode. Preferably the working electrode is a lead electrode. By electrodepositing lead onto a lead electrode, the deposited reduced lead may be collected along with the electrode as a larger piece of lead, thus the lead from the lead-based material is recycled into a larger piece of lead that is ready for use in the lead industry. This avoids the need for additional processing steps to separate the lead from the electrode. Preferably the working electrode is a lead foil electrode.

(26) In some embodiments, after deposition of the lead, it may be beneficial to wash the deposited lead metal. This may aid in removing residual DES and avoid post-deposition oxidation of the lead material.

(27) A counter electrode is provided in the electrochemical cell to balance the working electrode. The counter electrode, may act as the other half of the cell. This counter electrode balances the charge added or removed by the working electrode. These two electrodes, the working and counter electrodes, make up a two-electrode electrochemical cell, where the reduction and oxidation half reaction take place at the working and counter electrode, respectively. The counter electrode may be a metal electrode, preferably a IrO.sub.2-coated Ti electrode.

(28) Optionally a third electrode may be provided. Accordingly, a three-electrode cell may be used comprising the working electrode, the counter electrode and a third electrode: a reference electrode, which may act as reference in measuring and controlling the potential applied to the working electrode. These three electrodes, the working, reference and counter electrodes, make up a three-electrode electrochemical cell. When used in a three-electrode cell, the counter electrode may be a metal electrode, preferably an IrO.sub.2-coated Ti electrode. When used in a three-electrode cell, the counter electrode may also be known as an auxiliary electrode. The reference electrode may be a quasi-reference electrode. The reference electrode may be a metal electrode, preferably Ag-wire quasi-reference electrode. Alternatively, a stable reference electrode may be prepared using a DES in the reference electrode.

(29) Reference is now made to the following examples, which illustrate the invention in a non-limiting fashion.

EXAMPLES

(30) The lead-based materials have been dissolved in the DES and the Pb firstly electrodeposited onto indium tin oxide (ITO) to demonstrate the Pb can be successfully electrodeposited onto an electrode, and secondly electrodeposited onto Pb foil for longer deposition periods to extract nearly all of the Pb from the DES. The consequence of this is that by electrodepositing Pb onto a Pb electrode, the Pb from the used lead-based material is recycled into a larger piece of Pb that is ready for use in the lead industry.

(31) The results presented here show the successful deposition of Pb films on ITO working electrodes following the dissolution of the Pb-based materials in a DES. ITO is used as the working electrode in this case to differentiate between the deposited Pb and the substrate itself. This acts as an proof of Pb extraction and deposition using a DES for each of the lead-based materials.

(32) Following the proof of Pb deposition on ITO, the technique has been applied more directly to lead acid battery and lead perovskite solar cell recycling. Using longer deposition times, and a Pb foil working electrode, an extraction of up to 96.4% of the Pb from dissolved PbSO.sub.4 has been achieved, essentially recycling nearly all of the Pb from PbSO.sub.4. The stripping of lead perovskite films on TiO.sub.2-coated FTO substrates (consistent with those used in lead perovskite solar cells) has been undertaken to demonstrate that this process can be applied to lead perovskite solar cell recycling.

Example 1: Preparation of Deep Eutectic Solvent and Electrochemical Cell

(33) The DES has been prepared by mixing the hydrogen bond donor ethylene glycol (EG) and quaternary ammonium salt choline chloride (ChCl), in a 2:1 mole ratio, at 60 C. forming a transparent, homogeneous liquid. To these specific amounts of PbSO4, MAPbI.sub.3, FAPbI.sub.3, MAPbI.sub.3-XCl.sub.X, PbTe, and PbO.sub.2 have been added, also at 60 C., and fully dissolved, or dissolved as far as possible.

(34) Three-electrode electrochemical cells have been prepared with an Ag-wire quasi-reference electrode and IrO.sub.2-coated Ti mesh counter electrode. The working electrodes used have been either indium tin oxide (ITO) or Pb foil. For all electrochemical processes the DES was maintained at 60 C. Pb electrodeposition from the DESs has been undertaken by applying a constant reduction potential, identified from cyclic voltammograms (CV), for a given amount of time. These have been undertaken on working electrodes of both ITO (to demonstrate the Pb is indeed electrodeposited from the DES), and on Pb foil for complete extraction of Pb from the DES for recycling. The working electrodes have been rinsed with isopropanol, following the depositions, to remove any residual DES. X-ray diffraction (XRD) and scanning electron microscopy (SEM) have been used to identify the Pb deposition on the working electrode.

Example 2: Lead Acid Battery Recycling

(35) The electrodes in a discharged lead acid battery are comprised of PbSO.sub.4. For this reason a PbSO.sub.4 DES was prepared as in Example 1 such that a mole ratio of 2:1:0.00057 (EG:ChCl:PbSO.sub.4) was achieved with 0.6 mol EG+0.3 mol ChCl+0.17 mmol PbSO.sub.4. Two separate experiments have been undertaken, firstly electrodepositing Pb on an ITO working electrode to demonstrate Pb deposition, and secondly a longer deposition on a Pb foil working electrode for complete Pb extraction from the dissolved PbSO.sub.4. The PbSO.sub.4 completely dissolved in the DES leaving a clear, colourless liquid.

(36) Pb Deposition

(37) Pb films have been electrodeposited onto ITO working electrodes in order to demonstrate that Pb can be extracted from the PbSO.sub.4 DES as metallic Pb.

(38) The reduction potential was identified from the CV in FIG. 1, at the peak labelled R. The peak labelled O in the CV is attributed to the deposited Pb being oxidatively stripped back into solution. Pb(II) to Pb reduction of dissolved PbSO.sub.4 was undertaken at 0.75 V vs Ag, the potential of the reduction peak, for incremental times from 1 minute to 60 minutes forming even, grey films on the ITO working electrode surface. XRD patterns of these films are presented in FIG. 2, and demonstrate that Pb has been successfully electrodeposited from the DES onto the ITO working electrode. FIG. 3 shows SEM images of the Pb films, it can be seen that the Pb deposits as a series of particles which grow with increasing deposition time.

(39) Complete Pb Extraction

(40) In order to extract all of the Pb from the PbSO.sub.4 DES a large area (7 cm.sup.2) Pb working electrode has been used. The deposition potential for Pb has been determined using linear sweep voltammetry (LSV) to only probe the reduction region, rather than the reduction and oxidation regions probed by a CV, in order to avoid oxidising and stripping the Pb electrode itself into solution. A suitable deposition potential was determined to be 0.5 V vs Ag. A long Pb deposition was undertaken for 120 hours to extract as much Pb as possible from the DES. Additionally a 1 hour deposition was carried out to study the Pb deposition on Pb over shorter time scales. FIG. 4 shows SEM images of the Pb foil pre-deposition, following the 1 hour deposition and the 120 hour deposition. An additional control 120 hour deposition was undertaken to demonstrate that significant levels of Pb do not leach from the working electrode into solution, and to study the current-time characteristics of the current flow through the EG+ChCl.

(41) TABLE-US-00001 TABLE 1 Pb Concentration Solution (ppm) 0.6 mol EG + 0.3 mol ChCl + 0.17 mmol PbSO.sub.4 469 (Pre-deposition) 0.6 mol EG + 0.3 mol ChCl + 0.17 mmol PbSO.sub.4 17 (Following 120 hour deposition) 0.6 mol EG + 0.3 mol ChCl 0.05 (Pre-control deposition) 0.6 mol EG + 0.3 mol ChCl 0.84 (Following 120 hour control deposition)

(42) Inductively coupled plasma optical emission spectrometry (ICP-OES) measurements have been undertaken to measure the parts per million (ppm) and calculate the percentage of Pb removed from the DES, the results of which are displayed in Table 1. 96.4% of the Pb has been extracted from the DES within the 120 hours. From the concentrations in the control deposition it can be seen that only minimal Pb has leached from the working electrode into the DES (<1 ppm).

(43) From the SEM images of the Pb foil pre- and post-deposition (FIG. 4) it can be seen that the Pb first deposits (after 1 hour) as a series of particles, similar to those on ITO (FIG. 3), which then grow to form much larger structures following 120 hours of deposition. The XRD patterns in FIG. 5 demonstrate that the deposition occurs as metallic Pb on the Pb foil. There is a slight addition of PbO appearing following the 120 hour deposition, this is attributed to residual DES trapped on the substrate surface causing some oxidation post-deposition and could be dealt with by rinsing following the Pb deposition.

Example 3: Lead(IV) Oxide Recycling

(44) A DES system was prepared according to Example 1 such that the solution was comprised of 0.6 mol ethylene glycol+0.3 mol choline chloride+0.17 mmol PbO.sub.2, at a 2:1:0.00057 mole ratio.

(45) A three electrode electrochemical cell was prepared using with an Ag wire quasi-reference electrode and IrO.sub.2-coated Ti mesh counter electrode. The working electrode used was ITO. For all electrochemical experiments, the DES was maintained at 60 C.

(46) Pb Deposition

(47) A cyclic voltammogram (CV) of the ITO working electrode in the PbO.sub.2 DES was recorded to identify the reduction potential at which Pb is deposited on the working electrode. The CV is displayed in FIG. 6. A reduction peak can be observed at approximately 0.78 V vs Ag.

(48) Pb has been potentiostatically deposited on the ITO working electrode by applying a potential of 0.9 V vs Ag for 60 minutes. This potential is used to overcome the reduction potential, whilst remaining within the electrochemical window of the ITO. Following the 60 minutes of deposition a grey film was observed on the ITO working electrode. FIG. 7 shows an x-ray diffraction (XRD) pattern of the deposited Pb, demonstrating that metallic Pb has been successfully deposited.

(49) An SEM image of the Pb film deposited from the PbO.sub.2 DES is presented in FIG. 8. It can be seen that the Pb deposits as a series of particles on the ITO surface.

(50) The deposition potential for Pb on an ITO working electrode for PbO.sub.2 dissolved in an EG and ChCl DES has been identified from a CV. By applying a potential equal to, or in excess of, the reduction potential Pb has been potentiostatically deposited on the ITO surface. The deposited material has been confirmed as Pb through XRD and observed to deposit as a series of particles through SEM.

(51) This system acts as a proof of principle that Pb can be deposited on a metallic working electrode from PbO.sub.2 dissolved in a DES, and therefore the technique has application to lead-winning from spent lead acid batteries with the dissolved PbO.sub.2 being electrodeposited onto Pb foil working electrode, as has previously been demonstrated for the PbSO.sub.4 system.

Example 4: Lead Perovskite Photovoltaic Recycling

(52) The recycling of lead perovskite photovoltaic materials (MAPbI.sub.3, FAPbI.sub.3 and MAPbI.sub.3-XCl.sub.X) has been studied firstly by dissolving powdered perovskites in EG+ChCl such that a mole ratio of 2:1:0.00057 (EG:ChCl:Pb Perovskite) was achieved for consistency with the PbSO.sub.4 DES. CVs have been recorded to identify the reduction potential of Pb(II) to Pb for Pb deposition on an ITO working electrode, subsequently Pb has been potentiostatically deposited on the ITO to demonstrate Pb extraction. Pb has then been potentiostatically deposited on a Pb foil working electrode to demonstrate the complete extraction of Pb from the solution.

(53) In a lead perovskite solar cell the perovskite material is deposited on a TiO.sub.2-coated FTO substrate, therefore lead perovskite films on these substrates have been stripped in the EG+ChCl DES to demonstrate how the recycling process can be applied to perovskite solar cell.

(54) Pb Deposition

(55) For each of the three perovskite powders, when added to the EG+ChCl DES, complete dissolution was achieved and the liquid formed a translucent yellow colour. FIG. 9 (a) shows CVs using an ITO working electrode in the DESs in which each of the lead perovskites have been dissolved, as well as a blank control DES in which no perovskite was dissolved. As with the PbSO.sub.4 DES, one reduction peak (R) and one oxidation peak (O) is observed for the perovskite DESs, and in the control DES no peaks are present. The reduction and oxidation peaks are attributed to the deposition and stripping of Pb.

(56) Potentiostatic deposition of Pb on ITO was carried out from each lead perovskite DES for 60 minutes at a potential of 0.8 V vs Ag. From each lead perovskite DES an even grey film was electrodeposited on the ITO working electrode. FIG. 9 (b) shows XRD patterns of the deposited Pb. In all cases strong Pb peaks can be observed, demonstrating that crystalline Pb has been deposited.

(57) FIG. 10 shows an SEM film representative of those deposited from the lead perovskite DESs, for the MAPbI.sub.3-XCl.sub.X DES, demonstrating that the Pb deposits as a series of particles on the working electrode, consistent with that observed for the PbSO.sub.4 DES.

(58) Through the combination of CVs, potentiostatic deposition and characterisation with XRD and SEM it has been demonstrated that the lead perovskites MAPbI.sub.3, FAPbI.sub.3 and MAPbI.sub.3-XCl.sub.X can be dissolved in an EG+ChCl DES and the Pb can be extracted through electrodeposition on a working electrode of ITO.

(59) Complete Pb Extraction

(60) Using a large area Pb foil working electrode, of 7.5 cm.sup.2 in size, potentiostatic deposition has been undertaken on the DES solutions containing the dissolved powdered perovskites. The electrodeposition was carried out, on each solution, for 120 hours by applying a potential of 0.9 V vs Ag with the DES maintained at 60 C.

(61) The Pb concentration in each DES was measured before and after the Pb extraction using ICP-OES analysis. The results of these measurements are displayed in Table 1.

(62) TABLE-US-00002 TABLE 2 Pb Concentration Pb Concentration Percentage of Pb Pre-Extraction Post-Extraction Removed Solution (ppm) (ppm) (%) MAPbI.sub.3 432.80 1.37 99.7 DES Solution FAPbI.sub.3 540.34 6.86 98.7 DES Solution MAPbI.sub.3XCl.sub.X 616.49 1.43 99.8 DES Solution

(63) The results demonstrate that between 98.7% and 99.8% of the Pb in solution has been successfully extracted.

(64) Perovskite Film Stripping

(65) The applicability of the perovskite dissolving and Pb electrodeposition technique using the DES to perovskite solar cell recycling is demonstrated by the use of films of MAPbI.sub.3, FAPbI.sub.3 and MAPbI.sub.3-XCl.sub.X rather than powders. The films have been prepared on TiO.sub.2-coated FTO substrates (the typical structure used in perovskite solar cells) and have been held in the EG+ChCl DES at 60 C. for 30 minutes, with a gentle stirring applied. The lead perovskite films were dark brown in colour prior to dipping in the DES however once placed in the DES the dark brown colour was observed to quickly disappear as the films dissolved.

(66) The XRD patterns in FIG. 11 show each of the perovskite films before and after stripping as well as fresh FTO and TiO.sub.2-coated FTO substrates for comparison. It is clear that following 30 minutes of dissolution in the DES the perovskite films have all been completely removed, leaving only the TiO.sub.2-coated FTO which itself is not dissolved. Post-stripping of the lead perovskite the TiO.sub.2-coated FTO substrates have near identical XRD patterns to those prior to the deposition of the lead perovskite films.

(67) FIG. 12 shows SEM images of the fresh TiO.sub.2-coated FTO substrate as well as each of the three perovskite films before and after stripping in the DES. In each case the perovskite film has clearly been removed leaving only the fractured crystal-like structure of the TiO.sub.2-coated FTO. The visual differences in the TiO.sub.2 could be due to slight differences in the fabrication of the TiO.sub.2 layers before the perovskite is deposited. In any case the perovskite layer on top of the TiO.sub.2 is completely removed.

(68) The combination of the XRD and SEM results in FIGS. 11 and 12 demonstrate that the lead perovskite films can be completely removed from the TiO.sub.2-coated FTO substrates allowing for the safe recycling of the Pb and the re-use of the TiO.sub.2-coated FTO in new solar cells.

Example 5: Lead Telluride Thermoelectric Recycling

(69) Powdered PbTe was added to the EG+ChCl such that a DES of 0.6 mol EG+0.3 mol ChCl+0.17 mmol PbTe was produced, maintaining the 2:1:0.00057 mole ratio used throughout. After several hours of heating stirring at 60 C. the DES had formed a white colour due to incomplete dissolution of the PbTe.

(70) A CV of the DES was recorded using an ITO working electrode (displayed in FIG. 13) which demonstrates a reduction peak (R) similar to those from the PbSO.sub.4 and lead perovskite DESs, which is likely to be dissolved Pb(II) reducing to Pb at the ITO surface. A double oxidation peak (O) is observed which is due to the oxidation of the reduction product formed at R, this is demonstrated in the first cycle of the CV where the oxidation potential is swept through before the reduction potential and no peaks occur as the reduced species has not yet formed.

(71) Potentiostatic deposition was carried out at 0.62 V vs Ag for 60 minutes and 180 minutes. Some black material formed on the ITO surface, which delaminated when rinsing away the residual DES. SEM images (FIG. 15) indicated some Pb deposition.

(72) Embodiments of the invention have been described by way of example only. It will be appreciated that variations of the described embodiments may be made which are still within the scope of the invention.