US20130126354A1 - Electrolyte separation wall for the selective transfer of cations through the wall, manufacturing process and transfer process - Google Patents

Electrolyte separation wall for the selective transfer of cations through the wall, manufacturing process and transfer process Download PDF

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US20130126354A1
US20130126354A1 US13/811,434 US201113811434A US2013126354A1 US 20130126354 A1 US20130126354 A1 US 20130126354A1 US 201113811434 A US201113811434 A US 201113811434A US 2013126354 A1 US2013126354 A1 US 2013126354A1
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transfer
wall
electrolyte
cations
active layer
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Jean-Marie Lecuire
Sakina Seghir
Clotilde Boulanger
Sebastien Diliberto
Jose Lopez
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Universite de Lorraine
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Universite de Lorraine
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H01M50/437—Glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to an electrolyte separation wall for the selective transfer of cations through the wall, a manufacturing process for the said wall and a selective cation transfer process through the said wall.
  • the invention also relates to an electrolytic type process ensuring transfer of cations, through an adapted wall, from a first electrolyte solution containing one or more categories of ions of same charge or of different charges to a second electrolytic solution.
  • x being a number varying typically between 0 and 4.
  • the transfer wall is placed between two compartments including respectively a platinum-coated titanium electrode which operates as anode and a stainless steel electrode which operates as cathode.
  • the first compartment contains a first electrolyte which contains various cations of an effluent to be treated.
  • the second compartment contains a second electrolyte intended to receive the selected cations.
  • a direct electrical current is established between the anode and the cathode.
  • intercalation of the cation occurs at the M x Mo 6 S 8 /first electrolyte interface (effluent to be treated, mix of cations M n+ , M′ n+ , M′′ n+ different from each other for example), according to:
  • the mobility of the metallic cation in the Chevrel phase thus allows the transfer of the disolvated cation M n+ from one medium to the other without the transfer of any other chemical species from one or the other of the compartments.
  • a transfer wall in disc form is obtained by hot sintering of a composition powder mix adapted to the stoichiometry of the material required.
  • discs of active material with a thickness of 2 to 5 millimetres are obtained.
  • Lithium is, however, increasingly demanded in industry, especially for electric car batteries.
  • the aim of the invention is therefore to provide a selective transfer wall allowing a good transfer rate and with an enlarged choice of transferable cations.
  • the subject of the invention is an electrolyte separation wall including a sealed active layer made of a material capable of developing intercalation and deintercalation reactions for the selective transfer of cations through the wall, characterised in that it includes a support layer consisting of a porous material acting as support for the active layer.
  • the inventors have succeeded in making a wall with a porous support which provides the mechanical strength and an active layer the thickness of which can be very low. They have observed that the porous support does not obstruct the electrochemical reactions which occur at the level of the active layer. By reducing the thickness of the active layer, the transfer rate achieved is well above the rate limit according to prior art which is one of the targets of the invention.
  • the porous material is chosen, for example, among mullite, silica, glass fibre, quartz or a ceramic. These materials offer the qualities required to fulfil the role of the wall, that is, the mechanical strength, resistance to the products contained in the electrolytes and porosity.
  • the porosity of the porous material is for example between 0.4 and 0.6. This value expresses the ratio of material in relation to the volume taken up. It comprises a good trade-off between the volume of the electrolyte present in the porous support and the mechanical strength of the said support.
  • the material of the active layer is a binary or ternary material behaving as a host network with cation reversible accommodation properties according to an oxidation-reduction reaction.
  • the material of the active layer is for example a metallic chalcogenide.
  • the metallic chalcogenide is a chalcogenide with molybdenum clusters (Mo n X n+2 or M x Mo n X n+2 ), X being a chalcogene taken among S (Sulphur), Se (Selenium) and Te (Tellurium), and M being a metal.
  • the number n is chosen for example among 1, 1.5, 2, 3, 4, 5, 6 and 9.
  • the material of the active layer is a compound of lithium and a metal in oxide form, phosphate or fluoride or a combination of these forms, the metal being chosen among nickel, cobalt, iron, manganese, vanadium, titanium and chrome. It can be seen that these materials are capable of developing intercalation and deintercalation reactions and of transferring cations selectively, especially lithium.
  • a solution is prepared including an active material in powder form, a binder and a solvent, then the surface of a support layer made of a porous material is coated with the said solution and the solvent is evaporated to form a sealed active layer on the support layer.
  • the active layer obtained is sealed which guarantees that the electrolytes do not mix when the wall separates them. Also, in spite of the initial powder formulation, the active layer is electrically conductive which shows that the grains are in contact with each other and allow the oxidation-reduction reactions to develop over the complete surface area of the active layer. The layer obtained is very fine in compliance with the target fixed at the start.
  • the binder is for example poly(vinylidene fluoride).
  • the solvent is for example 1-methyl-2-pyrrolidone.
  • the material in powder form has, for example, a grain size between 30 and 100 ⁇ m.
  • the solution includes, among other things, graphite in powder form. This allows the electrical conductivity of the active layer to be completed.
  • the active layer is polished until the support layer appears through the active layer. This thus reduces the thickness of the active layer.
  • the subject of the invention is also a selective cation extraction process by electrochemical transfer characterised in that it uses as electrolyte separation wall a transfer wall as described above and transfer of the cations is ensured through the said transfer wall by generating a potential difference between, on the one hand, the first electrolyte and, on the other hand, the second electrolyte or the said transfer wall to induce an intercalation of the cations in the transfer wall on the side of the first electrolyte, a diffusion of the cations in said wall then their deintercalation in the second electrolyte.
  • the electrolytes is non-aqueous.
  • the electrolytes can be different between the compartments, notably by differentiation of the nature of the background salts, by their levels of acidity, by the presence of complexants, by the nature of the solvents notably mineral or organic non-aqueous solvents such as, for example, DMSO, DMF, ionic liquids, solid electrolytes, etc.
  • the transfer wall is electrically connected to a device measuring the potential between the said wall and reference electrodes located respectively in each electrolyte and the potential applied between the said electrolytes is adjusted to suit.
  • the potential difference is generated between the first electrolyte and the transfer wall and the deintercalation of the cations on the side of the second electrolyte is a chemical deintercalation by a chemical oxidising agent in the second electrolyte.
  • a succession of cation transfers is ensured through transfer walls arranged successively between end electrolytes and with one or more intermediary electrolytes between the various transfer walls.
  • the transferred metal is electrodeposited on the cathode. at least two transfer walls of different natures separate the first compartment from respective compartments in parallel for selective transfers of different cations with specific modulated intercalation electrolyses on each of the transfer walls engaged.
  • the transfers to separate compartments allow the specific simultaneous recovery of each of the metals, for example, for a source solution containing Lithium and Cobalt ions with use of an active layer made of Mo 6 S 8 for the transfer of the cobalt and a second layer made of LiMn 2 O 4 selective transfer of lithium.
  • FIG. 1 is a cross-sectional view of a transfer wall in compliance with the invention
  • FIG. 2 is an X-ray diffraction analysis graph of the porous material for the manufacture of a wall according to FIG. 1 ;
  • FIGS. 3 and 4 are schematic views of a test setup to check the porosity or the sealing of the wall of FIG. 1 ;
  • FIG. 5 is a schematic diagram of the device
  • FIG. 6 shows an arrangement using several compartments and transfer walls in series
  • FIG. 7 shows an arrangement using several compartments and transfer walls in parallel.
  • a transfer wall in disc form 2 in compliance with the invention is formed of a porous support 21 on which a fine active layer 22 is deposited.
  • the manufacture of sealed discs is done, in a first phase, by the manufacture of the porous support 21 and, in a second phase, by the application of the active layer 22 to the support 21 .
  • the porous support 21 is commercially available in mullite, quartz or ceramic.
  • an embodiment is detailed below, which is taken from the protocol given by the article by Garcia-Gabaldon et coll. on the manufacture of ceramic membranes based on kaolin and alumina developing a modulable porosity for their applications as separation membranes in electrochemistry: Effect of porosity on the effective electrical conductivity of different ceramic membranes used as separators in electrochemical reactors, Journal of Membranes Sciences 280 (2006) 536-544.
  • Kaolin hydrated aluminium silicate
  • the powder mix is homogenised in a porcelain mortar then wet with a minimum volume of acetone to prevent aggregates from forming. This mix is dried in free air for 14 h.
  • the powder obtained is then reground manually in the mortar for 10 minutes then by fractions of around 1 g, it is formed into discs by pressing in a 25 mm diameter die under a pressure of 2 tonnes for 5 minutes.
  • the compacted discs are 1 mm thick.
  • the samples are submitted to two successive heat treatment operations.
  • a first heating operation to 300° C. allows the oxidation in air of the potato starch. This organic binder is eliminated in 1 hour and thus creates the porosity. An additional treatment at 1100° C. for 8 to 24 hours ensures a satisfactory mechanical strength. After this heat treatment, two discs are obtained with a diameter of 24 mm and a thickness of 1 mm. The surface area is 4.5 cm 2 .
  • FIG. 2 An analysis by X-ray diffraction has been done on the porous disc ( FIG. 2 ). The spectrum recorded shows that there are no impurities and the formation of an alumina phase and of a mullite phase.
  • the evaluation of the porosity of the disc was tested using pH paper and nitric acid HNO 3 in the following manner shown on the diagram of FIG. 3 : the change in colour of the pH paper has confirmed the correct porosity of the disc.
  • the porosity checks give average values of 0.553 in volume for initial potato starch contents of 10% and 0.501 for contents of 5%.
  • the second phase in the manufacture of the disc consists in the physical coating of one face of the porous support 21.
  • the coating is done with a Chevrel phase suspension, formula Mo 6 X 8 , where X is a chalcogene, in a volatile solvent.
  • the working electrode is prepared from pulverulent compounds Mo 6 S 8 or Mo 6 Se 8 which comprise the active mass.
  • the Mo 6 Se 8 phase is obtained from a ceramic synthesis from the Mo o +2MoSe 2 mix homogenised and compressed cold into cylinders at a pressure of 250 MPa, done in sealed molybdenum crucible in arc furnace, under partial argon pressure, then heated for 50 h at 1300° C. The same grinding 50 ⁇ m screening treatment is also applied to this compound.
  • the purity of the synthetic powders is checked by their X-ray diffraction diagrams obtained on a diffractometer.
  • the synthesis of the sulphur-based Chevrel phase is done by means of a ternary phase with an intermediate metal such as, for example, Cu 3 Mo 6 S 8 .
  • the synthesis of this ternary compound is done in sealed silica tubes in a vacuum at 1000° C. for 50 h.
  • the initial mix is comprised of micrometric powders of Cu, MoS 2 and Mo homogenised in a ball grinder for 30 minutes and compressed cold under a pressure of 250 MPa.
  • the molybdenum powder is deoxidised under hydrogen current at 1000° C. for 3 h and the MoS 2 powder is prepared in sealed silica tubes by gradually heating the stoichiometric mix of the elements up to 800° C.
  • the grain size of the pulverulent products engaged is within a range of 30 to 100 micrometres.
  • the Mo 6 Se 8 phase is obtained from a ceramic synthesis from the Mo+2MoSe 2 mix homogenised and compressed cold into cylinders at a pressure of 250 MPa, done in sealed molybdenum crucible in the arc furnace, under partial argon pressure, then heated for 50 h at 1300° C.
  • the purity of the reaction products obtained is checked by their X-ray diffraction diagrams obtained on a diffractometer.
  • a suspension consisting of 95% Chevrel phases in powder form and 5% PVDF is formed in the 1-methyl-2-pyrrolidone, called NMP below, with 0.1 g of the solid Mo 6 X 8 phase, 0.005 g of PVDF dispersed in 1 ml of NMP. The whole is stirred for 2 hours.
  • Coating techniques using the spin-coating principle have also been used. They give coats of the same configuration as previously.
  • the wall is manufactured with as active material a matrix meeting the general Li X M Y O Z formula where y and z are integers, for example, including but not limited to Li x CoO 2 , LiMn 2 O 4 , LiV 3 O 8 , LiNiO 2 or LiMnO 2 .
  • the active material can also include a mix of metals M. The manufacturing principle remains a coating of the porous support by an Li X M Y O Z suspension.
  • the coating solution is prepared from a pulverulent mix Li X M Y O Z which comprises 80% in weight of the active material, 10% PVDF which plays the role of the binder and 10% carbon which ensures the electrical conductivity.
  • the mix is thoroughly homogenised in a mortar.
  • a suspension is made in the 1-methyl-2-pyrrolidone with stirring for 2 hours with 0.2 grams of powder mix for 1 ml of NMP.
  • the diagram on FIG. 5 shows a device for implementing a selective transfer process using transfer walls according to the invention.
  • the device includes a tank 1 including two compartments 11 and 12 , adapted to accommodate an electrolyte and separated by a separation wall 13 in which is placed a transfer wall 2 consisting of a disc 2 , installed in a sealed manner in the wall 13 .
  • the device also includes an anode A 1 placed in the first compartment 11 and a cathode C 2 placed in the second compartment 12 .
  • a potential difference AE can be applied between the anode Al and the cathode C 2 by means known themselves to impose and check a current i between the electrolytes E 1 and E 2 .
  • the active layer 22 is placed on the side of the first compartment 11 , even if the system also operates when it is placed on the side of the second compartment 12 .
  • a spring-mounted mobile contact system 44 ensures an electrical connection with the contour of the disc 2 covered by graphite lacquer and allows the disc to be connected to a control device, adapted notably to measure the interface potential Ei 1 , Ei 2 of the disc in relation to the reference electrodes 33 , 34 placed respectively in each compartment 11 , 12 of tank 1 , as shown on FIG. 5 .
  • the device is used as follows:
  • the compartments 11 and 12 are filled with the required electrolyte, for example, and in an in no way limitative manner, 100 ml of 0.5 M Na 2 SO 4 +M (i) SO 4 as first electrolyte E 1 in the first compartment 11 , and 100 ml of 0.5 M Na 2 SO 4 as second electrolyte E 2 in the second compartment 12 , with M (i) being one or more metallic cations that are to be separated.
  • the anode A 1 is placed in the first compartment 11 and the cathode C 2 in the second compartment 12 , and the contact 44 of the disc is connected with the potentiometric control means, connected to the reference electrodes 33 , 34 immersed in the electrolytes E 1 and E 2 .
  • the interface potentials can thus be checked and adjusted to suit the global potential ⁇ E applied between the anode A 1 and the cathode C 2 , to obtain a current density related to the operational surface area of the transfer wall 2 , or of all of the transfer walls arranged in parallel included, for example, between 2 and 200 A/m 2 .
  • a global intensiostatic state is established between the anode A 1 and the cathode C 2 .
  • RH for host network, the material of the active layer 22 .
  • the electrolyte E 1 being an original solution to be treated including a mix of cations of different metals and of identical or different charges, M n+ , M′ n+ , M′′ n′+ for example, and the electrolyte E 2 being a valorisation solution of metal M, the following occurs:
  • the mobility of the metallic cation in the host network thus allows the transfer of the disolvated cation M n+ from one medium to the other without transfer of any other chemical species from one or the other of the compartments.
  • the electrolytes placed in the two compartments 11 , 12 can be different, notably by the nature of the background salts, by the level of acidity, by the presence of complexants, by the nature of the solvents, notably organic or mineral non-aqueous solvents (DMSO, DMF, ionic liquids, solid electrolytes, etc.). It is thus possible, for example, to do an ionic transfer from a sulphate medium to a chloride medium without scattering of the said medium.
  • DMSO organic or mineral non-aqueous solvents
  • the tank includes three compartments.
  • the two end compartments 11 ′, 12 ′ are equivalent to compartments 11 and 12 of the example shown on FIG. 1 .
  • An additional compartment 15 containing an electrolyte E 3 , is located between the two compartments 11 ′ and 12 ′ and separated from these by separation walls 13 ′, 13 ′′ each including one or more transfer walls 2 ′, 2 ′′ according to the invention.
  • These transfer walls 2 ′, 2 ′′ can be of same nature, to simply increase the selectivity of the transfer from the compartment 11 ′ to the compartment 12 ′. They can also be of different natures and be managed differently by a specific check of the potentials applied between the various compartments for example to do a separation of different cations. For example, two types of cations can be transferred from the compartment 11 ′ to the compartment 15 , and only one from the compartment 15 to the compartment 12 ′.
  • Various combinations of discs and transfer parameters can thus be used to do the various required separations and treatments.
  • the intermediary electrolyte or electrolytes E 3 can also be identical to or different from one or the two electrolytes E 1 or E2.
  • the tank includes three compartments.
  • the central compartment 11 ′′ is equivalent to the first compartment 11 of the example shown on FIG. 2 .
  • the LH compartment 12 ′′ is equivalent to the second compartment 12 of the example shown on FIG. 2 .
  • An additional compartment 16 containing an electrolyte E 3 is located to the right of the first compartment and separated from it by a separation wall 13 ′′′ including one or more transfer walls 2 ′′′ according to the invention. These transfer walls 2 ′′′ are of different natures according to the separation wall 13 , 13 ′′′, to selectively transfer a specific cation for each compartment.
  • the first electrolyte El is a source solution containing cobalt and lithium ions.
  • the first transfer wall 2 between the first and the second compartments 11 ′′, 12 ′′, has an active material made of Mo 6 S 8 for the selective transfer of the cobalt
  • the second transfer wall 2 ′′′ between the first and the third compartments 11 ′′, 16
  • the first compartment 11 ′′ includes an anode A 1 ′′ in a manner to create a transfer current between the said anode A 1 ′′ and a cathode C 2 ′′ in the second compartment, and another transfer current between the said anode A 1 ′′ and a cathode C 3 in the third compartment 16 .
  • a porous disc 21 covered by a sulphur Chevrel phase based active layer 22 is used as transfer wall 2 , as described previously, in a setup in compliance with FIG. 5 .
  • the transfer of cations between the first compartment 11 , containing the first electrolyte E 1 (cation solution 0.1 M M 2+ in medium 0.1 M Na 2 SO 4 , 0.1 M H 2 SO 4 ) and the second compartment 12 containing the second valorisation electrolyte E 2 with 0.1 M Na 2 SO 4 and 0.1 M H 2 SO 4 has been studied for the two types of discs based respectively on Mo 6 S 8 and Mo 6 Se 8 , and at different current densities.
  • the aim of the study was to check, for different cations M n+ , the faradaic yields of the transfers, to determine the limit conditions for the porous Mo 6 S 8 and Mo 6 Se 8 discs and to evaluate the current density limit.
  • the transfer process is based on a preliminary conditioning with a quantity of inserted cations estimated from the Mo 6 X 8 mass deposited for a stoichoimetry of M x / 2 Mo 6 X 8 .
  • Tables 1 and 2 show the results obtained for an active material respectively Mo 6 S 8 and Mo 6 Se 8 .
  • the transfer rates in these selenium phases are located at the same order of magnitude as for the sulphur phase, that is 5.10 ⁇ 2 mol/h/m 2 for 3.2 A/m 2 and 4 mol/h/m 2 for 70 A/m 2 only for cations Cd 2+ , Zn 2+ , Mn 2+ , Cu 2+ , and In 3+ .
  • Tables 3 and 4 give the transfer rates for a current density of 70 A/m 2 for each element.
  • the first electrolyte E 1 contains a mix of cations only one type of which is transferred through the wall.
  • the selectivity is induced by the fact that during the electrolysis operation, the voltage applied between the two faces of the active layer 22 allows the intercalation and the deintercalation of only one type of cations.
  • a higher potential must be applied, which is not the aim of the process.
  • the type of cation which is transferred has a minimum intercalation potential and a maximum deintercalation potential which are expressed in relation to the reference potential given by a saturated calomel electrode (SCE).
  • SCE saturated calomel electrode
  • Transfer experimentations have been done for synthetic mixes of cations such as: Co/Ni, Cd/Zn, Cd/Ni, Zn/Mn, Cd/Co, Co/Fe, Ni/Fe and Cd/Co/Ni.
  • the transfer selectivity is expressed by a transfer selectivity rate of cation M n+ represented by the ratio M t n+ / ⁇ M it n+ of the quantity of cations transferred M t n+ for the species considered with the sum of cations transferred of all species M it n+ in the compartment 2 , for example Co t /(Co t +Ni t ) for the Co 2+ +Ni 2+ mix.
  • This ratio therefore approaches 100% as selectivity increases and takes a value of 50% if no selectivity develops.
  • Tables 5 and 6 give a summary of the selectivity rates obtained for the various mixes with different current densities. The values given for the different current densities correspond to the average of the selectivity rates obtained at each hour during the electrolysis of 1 to 7 hours.
  • the selectivity rate depends on the current density.
  • the selectivity is high for high current densities thus inducing high transfer rates.
  • the nature of the active layer 22 of the wall plays an important role in the selective transfer of cations.
  • the transfer selectivity of Cd 2+ or of Zn 2+ in the presence of Ni 2+ is truly improved up to 99% using a selenium matrix.
  • the same observation can be made for the case of Cd 2+ in the Cd/Co mix.
  • the selectivity is not affected by the low thickness of the active layer 22 .
  • the active layer 22 is made with material LiCoO 2 with a thickness of around 80 ⁇ m. Such a material is used for example in the positive electrode of lithium ion batteries.
  • the first electrolyte is a 1 M aqueous solution of Li + in 1M Na 2 SO 4 medium.
  • the second electrolyte which acts as valorisation solution is a 1M aqueous solution of Na 2 SO 4 . The results are given in table 7.
  • This example is similar to example 2, except that the second electrolyte which acts as valorisation solution is a solution of a propylene carbonate solvent and perchlorate ammonium tetrabutyl.
  • the anode is made of platinum-coated titanium and the cathode is made of stainless steel. The results are given in table 8.
  • Example 5 transfer of Li+ from a mixed Li 2 SO 4 and CoSO 4 electrolyte
  • the active layer is made with material LiMn 2 O 4 with a thickness of around 80 ⁇ m.
  • the first electrolyte is an aqueous solution containing cations Li + (1M) and Co 2+ (0.5M) in sulphate medium.
  • the second electrolyte which acts as valorisation solution is an Na 2 SO 4 solution with a concentration of 1M.
  • LiMn 2 O 4 on porous support Current density (A/m 2 ) 40 70 90 110 Lithium transfer faradaic 94 96 97 98 yield (%) Lithium transfer rate 1.43 2.24 3.06 3.67 (mol/h/m2)

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US13/811,434 2010-07-23 2011-07-06 Electrolyte separation wall for the selective transfer of cations through the wall, manufacturing process and transfer process Abandoned US20130126354A1 (en)

Applications Claiming Priority (3)

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FR1056066 2010-07-23
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PCT/FR2011/051602 WO2012010766A1 (fr) 2010-07-23 2011-07-06 Paroi de séparation d'électrolytes pour le transfert sélectif de cations à travers la paroi, procédé de fabrication et procédé de transfert

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CL2013000160A1 (es) 2013-08-23
WO2012010766A1 (fr) 2012-01-26
FR2963026A1 (fr) 2012-01-27
FR2963026B1 (fr) 2013-03-15
EP2595922A1 (fr) 2013-05-29
CA2805998A1 (fr) 2012-01-26
CN103153869A (zh) 2013-06-12
AU2011281483A1 (en) 2013-02-07

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