• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    electrochemical device having a solid ion conductive alkaline electrolyte and an aqueous electrolyte. The present invention relates to an alkaline cation conductive ceramic membrane covered on at least a portion of the surface thereof with a layer of organic cation conductive polyelectrolyte which is insoluble and chemically stable in water with basic pH. The invention also relates to an electrochemical device including a membrane such as a solid electrolyte in contact with a liquid electrolyte formed of an aqueous alkali metal hydroxide solution.
    公开号:BR112012010050B1
    申请号:R112012010050
    申请日:2010-10-21
    公开日:2019-12-03
    发明作者:Toussaint Gwenaëlle；Stevens Philippe
    申请人:Electricite De France；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for: "ELECTROCHEMICAL DEVICE HAVING A SOLID ION CONDUCTING ALKALINE ELECTROLYTE AND A WATER ELECTROLYTE". The present invention refers to an electrochemical device, in particular to a rechargeable battery, which includes both a solid electrolyte membrane that can conduct alkaline cations and an aqueous saturated electrolyte, these two electrolytes being separated from each other by an organic polymer film. The energy density per unit mass (expressed in Wh / kg) of batteries is still the main factor that limits their use in mobile devices, such as electric vehicles or portable electronics. The limited energy density of these batteries is mainly due to the performance of the materials from which they are made. The best negative electrode materials currently available generally have a specific capacity of 300 to 350 Ah / kg. The specific capacity is only about 100 to 150 Ah / kg for positive electrode materials. The advantage of metal-air systems (lithium-air or sodium-air) is that the positive electrode has an infinite capacity. The oxygen consumed in the positive electrode does not need to be stored in the electrode, but it can be obtained from the ambient air. The capacity of the battery, then, only depends on the capacity of the negative electrode and the capacity of the battery to store the product of oxygen reduction, that is, lithium or sodium hydroxide formed in the compartment of the positive electrode during the discharge of the battery. The air electrode requires a basic aqueous or acidic medium to operate optimally. Unfortunately, the metallic lithium or metallic sodium used for the negative electrode reacts very strongly with water, and it is impossible for it to form in the presence of water during recharge because the water reduces at voltages that are very very low, preventing the metal lithium or sodium forms. A waterproof physical barrier is therefore required between the negative electrode compartment, which is based on lithium or sodium metal, and the positive electrode compartment containing an aqueous electrolyte. This impermeable physical barrier however must selectively allow metallic cations to pass from the aqueous electrolyte to the negative electrode and in the opposite direction.
    A family of ceramic materials that meet these requirements, called "Li superionic conductors" (LISICONs) or "Na superionic conductors" (NASICONs), has been known for some time. These materials have advantageously high conductivities up to 1 χ 1CF4 or even 1 χ 10 ”3 S / cm at 25 ° C and good chemical stability with the aqueous electrolyte in the positive electrode compartment (air electrode). However, they react strongly with the lithium or sodium metal in the anode compartment and it is essential to isolate them, in a known way, from the lithium or sodium metal using a protective coating, for example a coating based on an oxynitrite glass phosphorous lithium (LiPON) or a glass of phosphorous sodium oxynitrite (NaPON).
    The first work done to develop a primary Li-air battery, that is, non-rechargeable, dates from the 70s (US 4,057,675). These batteries suffered from a high rate of self-discharge and a short service life due to corrosion (lithium reaction with water). A battery consists of six modules and delivers 1.2 kW of power, however it was produced (W. R. Momyer et al. (1980), Proc. 15th Intersoc. Energy Convers. Eng. Conf., Page 1480). A rechargeable Li / Ck battery without an aqueous phase, using an electrolyte made of a polymer containing a lithium salt, has also been produced (KM Abraham et al. (1996), <J. Electrochem. Soc. 143 (1 ), pages 1-5). The use of a positive electrode based on porous carbon in this cell gave good results in terms of oxygen reduction, but this electrode was not prepared for oxidation during recharge. It was possible to implement only three cycles and, to the Claimant's knowledge, no other work was published. Finally, more recently, the company PolyPlus reported obtaining a good performance with a Li-metal / non-rechargeable water battery using a separator based on LISICON (SJ Visco et al., Proc. 210th Meeting of the Electrochem. Soc., (2006), page 389).
    As explained above, one of the factors that limit the capacity of rechargeable metal-air batteries is their ability to store the alkali metal hydroxide formed during battery discharge, by reducing the oxygen in the positive electrode compartment (O2 + 4e ~ + 2H2O -> 4OH "), oxidation of the alkali metal in the negative electrode compartment (4Li -> 4Li + + 4e") and migration of the alkali metal ions thus formed in the positive electrode compartment. The concentration of alkali metal hydroxide in the aqueous electrolyte, therefore, increases during battery discharge and decreases during battery charging when alkalies migrate back into the negative electrode compartment, to be reduced here, and hydroxyl ions are oxidized on the oxygen evolution electrode (the positive electrode acting during battery charging).
    In order for the battery to have the largest possible capacity per unit weight, it is desirable to considerably limit the volume of aqueous electrolyte and to use solutions that are as concentrated as possible. In theory, there is no reason why the concentration of alkali metal hydroxide should not reach and exceed the saturation concentration (5.2M LiOH 20 ° C), above which limits the precipitated alkali metal hydroxide. The formation of a precipitate in principle is not a problem because when the battery is recharged, the precipitate can dissolve again and release lithium or sodium ions. The alkali metal hydroxide precipitate is therefore an advantageous storage of lithium or sodium ions.
    However, the Applicant, in the context of the investigation with the objective of continuously improving the performance of rechargeable metal-air batteries, has in fact observed a very substantial increase in the cationic resistance of the system, at the interface between the solid electrolyte membrane and the aqueous electrolyte, when alkali metal hydroxide precipitates in the aqueous electrolyte. This spectacular and highly undesirable decrease in cationic conductivity was attributed to a dense crystalline layer of alkali metal hydroxide (LiOH or NaOH) forming on the surface of the solid electrolyte membrane, such a layer does not conduct cations. This problem is particularly significant and acute for lithium hydroxide, which has a solubility in water at 20 ° C of only about 5.2 mol / liter. It is less of a problem for sodium hydroxide, which has about five times more water solubility than lithium hydroxide. The present invention is based on the discovery that the undesirable formation of such a dense crystalline layer of LiOH or, to a lesser extent, NaOH, at the solid electrolyte / aqueous electrolyte interface, can be prevented entirely by placing a thin layer of a suitable organic polymer to that interface.
    Therefore, an object of the present invention is a ceramic membrane that can conduct alkaline cations and is covered, on at least part of at least one of its surfaces, with a layer of an organic cation-conducting polyelectrolyte, said layer being insoluble and chemically stable in water at basic pH, even very basic pH, that is, water with a pH greater than 14. The ceramic membrane that can conduct alkaline cations is preferably a ceramic membrane that can conduct sodium ions or ions lithium, preferably lithium ions. These membrane ceramics that can conduct metal ions are known and sold, for example, as Lithium-ion-conducting glass-ceramics (LICGC) by Ohara Inc. (Japan). These glass-ceramics are ceramics with a chemical formula Lii + x (M, Ga, Al) x (Gei_yTiy) 2-X (PO4) 3 where m represents one or more metals chosen from Nd, Sm, UE, Gd, Tb, Dy, Ho, Er, Tm and Yb and where 0 x 0.8 and 0 y E 1.0. Ceramic membranes of this type are also known in the literature as superionic lithium conductors (LISICONs).
    Ceramics that can conduct sodium ions are, for example, materials with a chemical formula Nai + xZr2SixP3-x0i2 where 0 x 3.
    These ceramics that can conduct metal ions are especially described in US Patent No. 6,485,622 and in the article by N. Gasmi et al. , J. of Sol-Gel Science and Technology 4 (3), pages 231-237 and are known in the literature as superionic Na conductors (NASICONs). The thickness of the ceramic membrane that can conduct alkali metal cations depends on the area of the membrane. The larger the area of the latter, the thicker the ceramic must be to be able to withstand mechanical stresses. However, electrochemical devices generally seek to use, as far as possible, fine solid electrolytes.
    This is because the electrical performance, of a cell or battery for example, is partly governed by the resistance of the electrolyte. This specific resistance (R) is expressed by the formula: R = (rxe) / A where r denotes the resistivity of the electrolyte, and its thickness and its area. In other words, the smaller the thickness and the electrolyte, the greater the energy efficiency of the device. The solid electrolyte membrane used in the present invention is advantageously from 30 pm to 500 pm in thickness and preferably from 50 pm to 160 pm in thickness. For areas significantly larger than a few cm2 the thickness of the membrane must therefore increase, or the membrane must be reinforced and supported by a reinforcing structure, for example resin strips or a resin grid attached to one or both sides of the membrane and leaving the largest possible area of the latter free, that is, at least 80% and preferably at least 90% of the surface of the solid electrolyte membrane.
    This ceramic membrane is coated on at least one of its surfaces with a layer of an organic cation-conducting polymer, the polymer being insoluble in water at basic pH and chemically stable at basic pH. The term "organic cation-conducting polymer" or "organic cation-conducting polyelectrolyte" is, in the present invention, understood to mean a polymer comprising a plurality of electrolyte groups. When such a polymer is put in contact with water, the electrolyte groups dissociate and the negative charge, associated with cations (counterions), appears in its main structure. The charge on the polymer depends on the number of electrolyte groups present and the pH of the solution.
    Such a cation-conducting polyelectrolyte, therefore, has an intrinsic ability to conduct cations and must be differentiated from solid electrolytes based on salt-impregnated polymers, such as lithium-metal-polymer (LMP) electrolyte batteries, for example, which consist of a neutral polymer, such as polyethylene oxide, impregnated with a lithium salt. These LMP-battery electrolytes would actually be unsuitable for the application envisaged in the present invention because they are soluble in water and chemically unstable in a highly basic medium.
    Such organic cation conducting polymers are known and are generally used in polymer electrolyte membrane fuel cells (PEMFC), or for chlorine / sodium hydroxide electrolysis, where they are used as a solid electrolyte. The term "water-stable polymer at basic pH" is, in the present invention, understood to mean a polymer which, when immersed in water of pH 14 at 50 ° C, does not exhibit detectable chemical degradation and no drop in ionic conductivity.
    As explained above, this polymer, which is insoluble and stable in water at basic pH, is a polyacid polyelectrolyte that has a number of negatively charged groups (anions). It is these negatively charged groups, linked to the main structure of the polymer and associated with cationic counterions, that are actually responsible for the cationic conductivity of the polymer layer that covers the ceramic. The organic polymer must be sufficiently conductive of Li + or Na + ions, but it is not necessary for it to be selective over a particular type of cation, this selectivity is in fact ensured by the underlying cation conducting ceramic.
    For the cationic conductivity of the organic polymer to be high enough, its equivalent weight (average molar mass per negatively charged group) must be low enough. This is because the lower the equivalent weight, the greater the ion exchange capacity of the polymer. In general, polymers with an equivalent acid group weight greater than 2000 g / mol, preferably 1800 g / mol, should not be used. The equivalent weight should not, however, be too low because, if the negative charge concentration is too high, there is a risk that the polymer will become soluble in water and in the aqueous electrolyte. However, it is difficult, even impossible, to define a lower limit for the equivalent weight of the polymer. Specifically, it should be understood that the lower limit of the equivalent weight range depends, inter alia, on the chemical nature of the polymer and, in particular, on the hydrophobicity of uncharged comonomers. Specifically, a polymer with a very hydrophobic backbone can remain insoluble in water, having an equivalent weight less than a polymer with a less hydrophobic backbone. A person skilled in the art will have no problem adjusting the equivalent weight of the polymer to the lowest possible value, which, however, preserves its insolubility in water. The equivalent weight of the acid group of the organic polymer is preferably between 600 and 1800 g / mol, in particular between 700 and 1500 g / mol. The organic polymer is preferably an organic halopolymer, and in particular a fluoropolymer is preferred. As indicated above, this polymer must carry acidic groups. These acid groups can be strong or weak acids, the generally very high pH of use guarantees a sufficiently high dissociation rate for weak acids.
    Mention should be made, by means of the particularly preferred example, of a copolymer of tetrafluoroethylene and a comonomer carrying an acid group, preferably a polymer with the chemical formula: where X represents a -C00 ~ group or a -SO3 ”group, of preferably a group -SC> 3 ~, and M + represents a proton or a metal cation.
    Such preferred polymers are known and have been commercially available for many years under the trade name Nafion®. Dispersions or solutions of the present polymer can be uniformly deposited on the ceramic membranes, for example by spraying, dip coating, centrifugal coating, roller coating or brush coating. After the solvent phase has been evaporated, the polymer-coated ceramic is preferably subjected to heat treatment, for example, for one hour at about 150 ° in air, in order to stabilize the polymer layer. After deposition, the polymer is in protonic form. The protons will be exchanged for Li + or Na + ions during immersion in sodium or lithium hydroxide solutions.
    For tetrafluoroethylene copolymers and an acid comonomer, as described above, the equivalent weight of the acid group is preferably between 1000 and 1200 g / mol. The thickness of the organic polymer layer after deposition, drying and an optional heat treatment is generally between 1 and 50 μΜ, preferably between 2 and 20 μΜ, and in particular between 2 and 10 μΜ. The polymer layer must be thick enough to be stable and cover the membrane and must effectively prevent crystallization of the alkali metal hydroxide. Larger thicknesses, that is, greater than 50 pm, can certainly be predicted, but have the disadvantage of increasing the resistance of the organic polymer layer undesirably.
    In one embodiment of the ceramic membrane of the present invention, the organic cation-conducting polymer that is insoluble and chemically stable in water at basic pH covers only one of the two surfaces of the ceramic membrane, and the other surface is covered with a protective coating with base in Li3N, Li3P, Lil, LiBr, LiF or lithium phosphorous oxynitrite (LiPON) or based on sodium phosphorous oxynitrite (NaPON), the coating preferably being a LiPON or NaPON coating. This coating protects the membrane from being attacked by the negative electrode materials. Such a three-layer sandwich structure (protective coating / ceramic membrane / organic polymer) will, in particular, be used in metal-air or metal-water cells or batteries where the solid electrolyte, ie the ceramic membrane, must be isolated from the alkali metal of the negative electrode compartment. The ceramic membrane described above which can conduct alkaline cations and which is coated with an organic cation-conducting polymer layer can, in principle, be used in all electrochemical devices which employ a solid electrolyte and a liquid aqueous electrolyte containing a high concentration of a compound susceptible to crystallize on the surface of the ceramic membrane if the latter is not covered with a polymer.
    Therefore, another object of the present invention is an electrochemical device containing: - as a solid electrolyte, a ceramic membrane that can conduct alkaline cations, a membrane being covered with an organic cation-conducting polymer that is insoluble and chemically stable in water at pH basic, as described above, and - as a liquid electrolyte, an aqueous solution of alkali metal hydroxide making contact with said organic polymer.
    This electrochemical device is preferably a rechargeable or non-rechargeable metal-air or metal-water battery, preferably a rechargeable or non-rechargeable lithium-air or lithium-water battery.
    A lithium-air battery according to the present invention comprises: a negative electrode compartment, containing lithium metal; - a positive electrode compartment comprising at least one positive air electrode immersed in an aqueous solution of lithium hydroxide, and - a solid electrolyte that hermetically and impermeatically separates the negative electrode compartment from the electrode compartment positive, said solid electrolyte being a ceramic membrane according to the present invention, covered with one of its surfaces (the surface facing the positive electrode compartment) with an organic cation-conducting polymer that is insoluble and chemically stable in water at basic pH and, optionally, if necessary, covered with the other surface (the surface facing the negative electrode compartment) with a protective coating based on Li3N, Lí3P, Lil, LiBr, LiF or lithium phosphorous oxynitrite (LiPON ), the coating preferably being one based on LiPON. The lithium-air battery, when it is a rechargeable battery, preferably, in addition, comprises a positive oxygen emission electrode (which is active during battery recharge), immersed, since the air electrode is in the electrolyte aqueous.
    A lithium-water battery according to the present invention differs from a lithium-air battery simply in that the air electrode, active during discharge, is replaced by a positive hydrogen-emitting electrode that catalyzes the reduction of water according to the reaction: 2H2O + 2e “H2 + 20H ~ The electrochemical device of the present invention can also be an electrolysis cell comprising a negative electrode compartment and a positive electrode compartment, the two compartments (half-cells) being separated from each other by a ceramic membrane, according to the invention, which can conduct alkaline cations. Such an electrolysis cell can be used, for example, to recover, from a lithium or sodium salt, lithium or sodium hydroxide and the acid corresponding to the anion of said salt. To do this, an aqueous solution of the salt in question, for example, Li2SO4, is introduced into the positive electrode compartment and a potential is applied between the two electrodes. At the end of the electrolysis reaction, the positive electrode compartment will contain a sulfuric acid solution and the negative electrode compartment will contain a LiOH solution and possibly a LiOH precipitate. In this embodiment of the device of the present invention, the membrane that can conduct alkaline cations is covered with organic polymer, at least, on its face facing the negative electrode compartment.
    Finally, the electrochemical device can be a lithium pump or a sodium pump, that is, an electrochemical device that allows lithium, preferably in the form of solid LiOH, or sodium, preferably in the form of a solid NaOH, to be selectively recovered and concentrated from a diluted or polluted aqueous solution. Such a lithium or sodium pump has a structure identical to that of an electrolysis cell, as described above, but works differently because the solutions introduced in the negative and positive electrode compartments are different. A diluted or contaminated solution containing the alkaline cation in question is introduced into the positive electrode compartment and a voltage is applied between the two electrodes. At the end of the electrochemical reaction, all alkali cations are in the form of alkali metal hydroxide (LiOH or NaOH) in the negative electrode compartment. As for the electrolysis cell described above, the surface of the ceramic membrane facing the negative electrode compartment is where the lithium or sodium hydroxide will accumulate and it is this surface that must be covered with organic polymer. The present invention is illustrated below using the accompanying figures, in which: Figure 1 shows the structure of a lithium-air battery according to the invention; and Figure 2 shows how the voltage required to maintain a current of 2 mA, in the tests described in the example below, varied over time.
    In figure 1, the negative electrode compartment comprises a negative electrode made of a lithium metal and connected to an electronic conductor 2. The positive electrode compartment includes a liquid electrolyte 3 consisting of a saturated LiOH solution, in which an electrode of air 4 and an oxygen emitting electrode 5 are immersed. A precipitate of LiOH 6 accumulates at the bottom of the positive electrode compartment. The two compartments are separated from each other by a ceramic membrane 7 covered, on the negative electrode side, by a protective coating based on LiPON 8, and, on the positive electrode side, with a layer of an organic cation-conducting polymer 9 which is insoluble in water. The coating 8 serves to isolate the ceramic membrane from the metallic lithium while the organic polymer layer 9 prevents the crystallized LiOH layer from forming on the surface of the ceramic membrane 7.
    Example To demonstrate the effect of placing a thin layer of hydrophobic, cation-conducting organic polymer on the surface of a ceramic electrolyte membrane, an electrochemical device was prepared comprising two compartments separated from each other by a ceramic membrane that could conduct ions Li + (LISICON membrane); the membrane was 300 mm thick and was sold by Ohara. Both compartments were filled with a 5M LiOH aqueous solution. A platinum electrode was inserted in each compartment. Using a potentiostat, a current of 2 mA was made to flow through the cell between the two platinum electrodes, thus causing Li + ions to pass from the anode compartment to the cathode compartment. The migration of Li + ions was accompanied by the formation of OH ~ ions in the positive electrode compartment by reducing water or oxygen. The positive electrode compartment of this device mimics the operation of the positive electrode compartment of a lithium-water battery or lithium-air battery at the interface between the LISICON ceramic and the aqueous electrolyte containing LiOH. The 2 mA current flow was maintained until LiOH saturation and precipitation occurred, and the voltage required to maintain a 2 mA current flow was measured throughout the experiment.
    After about 45 hours of operation, as LiOH began to precipitate, a rapid and significant increase in voltage required to maintain a current of 2 mA was observed (see curve A in figure 2).
    A visual analysis of the ceramic LISICON membrane showed that a dense layer of LiOH crystals formed on the surface of the membrane exposed to the saturated electrolyte in the positive electrode compartment. The same experiment was carried out with a LISICON ceramic membrane identical to the first, but covered, on the surface exposed to the positive electrode, with a layer of Nafion ®. Curve B in figure 2 shows the variation in voltage required to maintain a current of 2 mA. It will be seen that any increase in voltage was observed when LiOH started to precipitate in the positive electrode compartment. LiOH crystals were indeed observed to form in the positive electrode compartment, but these precipitated crystals fell to the bottom of the compartment and were not deposited on the surface of the Nafion ® layer covering the LISICON ceramic membrane.
    权利要求:
    Claims (18)
    [1]
    1. Ceramic membrane characterized by the fact that it can conduct alkali metal cations, a part of the membrane surface being covered with a layer of an organic cation-conducting polymer which is a polyacid polymer carrying a number of negatively charged groups that the polymer has an acid group of equivalent weight less than 2000 g / mol, the thickness of the ceramic membrane being from 30 μm to 500 μm, said layer being insoluble and chemically stable in water at basic pH.
    [2]
    2. Ceramic membrane according to claim 1, characterized by the fact that it is a ceramic membrane with the chemical formula: Li1 + x (M, Ga, Al) x (Ge1-yTiy) 2-x (PO4) 3, where M is a metal chosen from Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or a mixture of them, and where 0 <x <0.8 and 0 <y <1 , 0, or is a ceramic membrane with the chemical formula: Na1 + xZr2SixP3-xO12, where 0 E x E 3.
    [3]
    3. Ceramic membrane according to claim 1, characterized by the fact that the organic cation-conducting polymer is a halopolymer carrying acid groups.
    [4]
    4. Ceramic membrane according to claim 3, characterized in that the organic polymer is a copolymer of tetrafluoroethylene and a comonomer carrying an acid group.
    [5]
    5. Ceramic membrane according to claim 1, characterized by the fact that the organic cation-conducting polymer layer is 1 to 50 μm in thickness.
    [6]
    6. Ceramic membrane according to claim 1, characterized by the fact that one of its surfaces is covered with the organic cation-conducting polymer layer, and the other surface of the membrane is covered with a protective coating based on in Li3N, Li3P, LiI, LiBr, LiF or lithium phosphorous oxynitrite (LiPON) or based on sodium phosphorous oxynitrite (NaPON).
    [7]
    7. Ceramic membrane, according to claim 1, characterized by the fact that it is 50 μm to 160 μm in thickness.
    [8]
    8. Ceramic membrane according to claim 3, characterized by the fact that the organic cation-conducting polymer is a fluoropolymer carrying acid groups.
    [9]
    9. Ceramic membrane according to claim 4, characterized by the fact that the acid group is a -SO3-M + group.
    [10]
    10. Ceramic membrane according to claim 5, characterized by the fact that the organic cation-conducting polymer layer is 2 to 10 μm in thickness.
    [11]
    11. Ceramic membrane according to claim 6, characterized in that the coating is a LiPON or NaPON coating.
    [12]
    12. Electrochemical device, characterized by the fact that it contains: - as a solid electrolyte, a ceramic membrane that can conduct alkali metal cations, as defined in claim 1; and - as a liquid electrolyte, an aqueous solution of alkali metal hydroxide making contact with said organic polymer.
    [13]
    13. Electrochemical device, according to claim 12, characterized by the fact that it is a metal-air battery.
    [14]
    14. Electrochemical device according to claim 12, characterized by the fact that it is a metal-water battery.
    [15]
    15. Electrochemical device according to claim 12, characterized by the fact that it is an electrolysis cell.
    [16]
    16. Electrochemical device according to claim 12, characterized by the fact that it is a lithium bomb or a sodium bomb.
    [17]
    17. Electrochemical device according to claim 13, characterized by the fact that the metal-air battery is a lithium-air battery.
    [18]
    18. Electrochemical device, according to claim 13, characterized by the fact that the metal-water battery is a lithium-water battery.
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    申请号 | 申请日 | 专利标题
    FR0957528A|FR2951714B1|2009-10-27|2009-10-27|ELECTROCHEMICAL DEVICE WITH SOLID ELECTROLYTE CONDUCTING IONS ALKALI AND AQUEOUS ELECTROLYTE|
    PCT/FR2010/052246|WO2011051597A1|2009-10-27|2010-10-21|Electrochemical device having a solid alkaline ion-conducting electrolyte and an aqueous electrolyte|
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