• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a liquid cathode battery comprising: a calcium anode; an electrolyte comprising a sulfur or phosphorus oxidizing solvent and at least one salt; a cathode comprising, as active material, a compound identical to the aforementioned oxidizing solvent; characterized in that the salt is a strontium salt present at a concentration greater than 0.85 mol.L-1.
    公开号:FR3032559A1
    申请号:FR1551061
    申请日:2015-02-10
    公开日:2016-08-12
    发明作者:Eric Mayousse；Lionel Blanc；Benoit Chavillon；Philippe Chenebault
    申请人:Weapso；Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The present invention relates to a specific liquid cathode battery and, more specifically, to a liquid cathode and calcium anode battery operable over a wide range of temperatures. and especially in high temperature ranges, for example, from -40 ° C to +300 ° C and, more specifically, from -40 ° C to +250 ° C. Also, the present invention can find application in all fields requiring the production of electrical energy, in contexts where the temperature differences can be high but also in contexts where the temperature is particularly high, as is the case with drilling or monitoring wells production or geothermal, the batteries being, more specifically, used in this area to supply measurement systems. STATE OF THE PRIOR ART As mentioned above, the cells of the invention are based on the technology of liquid cathode batteries, which have the particularity that the active compound used at the cathode also fulfills the role of solvent of the electrolyte, one of the flagship models of this type of battery being the lithium-thionyl chloride battery. Thus, such a system 1 is conventionally composed, as illustrated in FIG. 1 appended hereto, of the following elements: a negative electrode (or anode) 3 made of lithium metal, in which the oxidation of lithium occurs according to the following reaction: Li Li + + e-3032559 2 -a positive electrode (or cathode) 5, generally comprising a carbonaceous matrix and, as active material, thionyl chloride, which is reduced according to the following reaction: 2 SOCl2 + 4e-S + SO2 + 4CI- 5-an electrolyte 7 disposed between said negative electrode and said positive electrode, which electrolyte comprises, as solvent, thionyl chloride, salts and optionally one or more additives, the negative electrode and the positive electrode being connected to an external circuit 9, which receives the electric current produced via the aforementioned electrodes 10. By combining the electrochemical reaction with the positive electrode and the electrochemical reaction with the negative electrode, the global reaction (called discharge) can be represented by the following equation: 4 Li + 2SOCl 2 S + SO 2 (gas) + 4 LiCl ( precipitated), the products of the reaction thus being sulfur, partially soluble in the electrolyte, SO 2 gas, which solubilizes in the electrolyte and a lithium chloride salt LiCl, which precipitates in the carbon matrix constituting the electrode positive. The electrolyte comprises, in addition to thionyl chloride, lithium salts, such as LiAlC14 or LiGaCl4, to promote the ionic conduction of the electrolyte and, optionally, additives to control the formation of the lithium passivation layer and to control self-discharge of the battery. The carbon matrix constituting the positive electrode serves, as mentioned above, at least in part, a recovery matrix of the reaction products and is composed, generally of a selected carbon material, for example, among the black d acetylene, the carbon fibers, which carbonaceous material is trapped by a binder, preferably inert, such as polytetrafluoroethylene, which allows the mechanical strength of the electrode. From the point of view of their electrochemical characteristics, the Li / SOCl2 cells have the following advantages: a thermodynamic voltage of 3.64 V per cell based on the free enthalpy variation due to the above-mentioned overall discharge reaction ; a high theoretical mass energy of 1470 Wh / kg (of the order of 5273 kJ / kg); A very low self-discharge phenomenon (evaluated at 1% capacity loss per year at a temperature of 20 ° C); an operating temperature ranging from -60 ° C. (limitation imposed by the electrolyte) to 180 ° C. (limitation imposed by lithium metal); and a low internal pressure, because the gaseous reaction products, such as SO 2, are partially soluble in the electrolyte. However, this system also has a certain number of drawbacks, in particular because of the reactivity of lithium metal with the humidity of air or water, to form hydrogen, lithium LiOH with production of heat. Moreover, a passivation layer is formed on the surface of the lithium (this layer comprising LiCl), which can cause a voltage drop during a current draw. Finally, as suggested above, the use of this system is theoretically limited to a temperature of 180 ° C., the melting point of the lithium above which short circuits occur generating a thermal runaway and a booster overpressure. battery, which can lead to its destruction. Also, at temperatures above 180 ° C, the use of such batteries is no longer possible because of the melting of lithium. In addition, the use of lithium anode batteries poses safety problems arising during their production, transportation, use or even recycling.
    [0002] In order to overcome these drawbacks, it has been proposed to use, as material constituting the negative electrode, a material based on a lithium alloy with a second metal which has a melting point higher than that of lithium metal alone. , an alloy of this type being an alloy of lithium and magnesium, as described in particular in US Pat. No. 5,705,293, and more specifically, alloys comprising a proportion of magnesium of 30%, which makes it possible to access temperatures 3032559 4 d use of 200-220 ° C. Indeed, the introduction of magnesium in this proportion induces a shift towards higher values of melting temperature, as evidenced by the Li / Mg phase diagram. However, given the strong internal resistance of these cells 5 comprising such an alloy at the negative electrode, it is necessary to condition them before use, these packaging operations may be restrictive for the user. On the other hand, in case of exceeding the melting temperature of the anode, these batteries may also present security problems. As an alternative, safer batteries 10 have also been proposed than lithium batteries, these cells operating with an anode, no longer made of lithium, but with calcium and a cathode based on thionyl chloride, this type of battery being called Ca cell / Thionyl chloride. In particular, Peled et al. (in J. Electrochem.Soc.Vol., 128, No. 9, 1936-1938 and J. Electrochem.Soc.Vol., 131, No. 10, 2314-2315) disclose Ca / thionyl chloride cells having a structural structure. said spiral, whose electrolyte comprises a salt of Ca type (AIC14) 2 at different concentrations. This battery definition made it possible to safely discharge batteries at room temperature. In this work, while the results look promising, there is still a need for solutions that provide similar performance to lithium-based batteries in terms of corrosion and conductivity. In order to improve the use of calcium to enter the anode constitution, Walker et al. (J. Electrochem.Soc., Vol 135, No. 10, pp. 2471-2472) have used an electrolyte still having a salt of the Ca (AIC14) 2 type, with a sulfuryl chloride type solvent, to which A SO 2 solution was added, which reduced the corrosion phenomenon and increased the operating voltage of the system. Alternatively, it has also been proposed to use, to form the anode, calcium alloys, such as calcium / lithium alloys (with 2% lithium) and calcium / antimony alloys (with 10% antimony), as stated in J. Electrochem. Sac. (139), 3129-3135, and with, for the electrolyte, thionyl chloride 3032559 containing Ca (AIC14) 2 or Li (AIC14) as the salt, although it has not been shown with these cells, high temperature performance. Finally, it has been tested, with calcium batteries, an electrolyte comprising, as salt, Ca (AlCl.sub.2) .sub.2, to which SO.sub.2 is added and as a cathode, a carbon electrode to which it has been added, for example, TiO4. These additives have above all allowed to demonstrate an increase in the conductivity of the electrolyte and thus to reach higher discharge currents, and at room temperature. In view of the drawbacks mentioned above, the authors of the present invention have therefore set themselves the objective of setting up a new type of calcium battery, this new type enabling use at temperatures exceeding 200 ° C. C in a secure way. SUMMARY OF THE INVENTION The inventors of the present invention have surprisingly discovered that by using a salt specific to a specific concentration in the electrolyte, it is possible to obtain effective performance at elevated temperatures. and exceeding 200 ° C. Also, the invention relates to a liquid cathode battery comprising: a calcium anode; An electrolyte comprising a sulfur and / or phosphorus oxidizing solvent and at least one salt; a cathode comprising, as active material, a compound identical to the aforementioned oxidizing solvent; characterized in that the salt is a strontium salt present at a concentration greater than 0.85 mol.L-1. Before going into more detail in the description of the invention, we specify the following definitions. By cathode is meant, conventionally, in the foregoing and the following, the electrode which is the seat of a reduction reaction, in this case, here, the reduction of the liquid cathode, when the battery flows current, that is to say when it is in the process of discharge. The cathode can also be described as a positive electrode. By anode is meant conventionally, in what precedes and what follows, the electrode which is the seat of an oxidation reaction, when the accumulator delivers current, that is to say when he is in the process of discharge. The anode can also be described as a negative electrode. By active material is meant, conventionally, in the foregoing and the following, the material which is directly involved in the reduction reaction occurring at the cathode. For the cathode, it conventionally comprises a porous matrix, for example a porous matrix made of a carbonaceous material, which makes it possible to receive the active material of the electrode and which can also make it possible to recover the reaction products of the electrode. the battery.
    [0003] More specifically, the porous matrix may be of a carbon material selected from carbon blacks, acetylene blacks, graphite, carbon fibers, and mixtures thereof. A polymeric binder (for example, polytetrafluoroethylene) can help to maintain the cathode. The porous matrix may be associated with a current collector substrate, which substrate may be of a metallic material (composed of a single metal element or an alloy of a metal element with another element), which is For example, in the form of a plate, a strip or a grid, a specific example of a current collector substrate may be a nickel grid. The anode is, for its part, a calcium anode (that is to say an anode exclusively composed of calcium). Calcium has the advantage of having a high melting point (of the order of 842 ° C.). In addition, calcium has a volume capacity of 2.06 Ah / cm3 equal to that of lithium. This allows, for equal volume, to introduce the same calcium capacity in a stack. As mentioned above, the electrolyte comprises a sulfur and / or phosphorus oxidizing solvent and at least one strontium salt included in the electrolyte at a concentration greater than 0.85 mol.L-1. sulfur and / or phosphorus oxidizing solvent also constituting the active material of the cathode. More specifically, the oxidizing solvent can be: a sulfur-containing solvent comprising one or more chlorine atoms, such as a solvent selected from thionyl chloride (SOCl 2), sulfuryl chloride (SO 2 Cl 2), disulfide dichloride (S2C12), sulfur dichloride (SC12); a non-chlorinated sulfur solvent, such as sulfur dioxide (SO 2); or a phosphorus and optionally sulfur-containing solvent comprising one or more chlorine atoms, such as phosphoryl trichloride (POCl3), thiophosphoryl trichloride (PSCI3). Preferably, the oxidizing solvent is thionyl chloride (SOCl2). As regards the strontium salt, it may be a salt comprising a strontium Sr 'cation associated with a halogenated anion (such as fluorine, bromine, chlorine or iodine) based on a chosen element. among aluminum, gallium, boron, indium, vanadium, silicon, niobium, tantalum, tungsten, bismuth. Advantageously, the halogenated anion is an anion based on chlorine. More specifically, and advantageously, it may be a salt of Sr strontium tetrachloroaluminate (AlCl 4) 2. The salt present in the electrolyte can result from the reaction of a Lewis acid and a Lewis base, this reaction can take place ex situ, that is to say before introduction into the cell or in situ, that is, within the cell, when the Lewis acid and the Lewis base are introduced into the cell. More specifically, the strontium salt can be made by reacting: a Lewis base SrX 2, wherein X is a halogen atom, such as a chlorine atom, a bromine atom, a fluorine atom , an iodine atom; and a Lewis acid chosen from an aluminum halide AIX3, a gallium halide GaX3, a boron halide BX3, an indium halide InX3, a vanadium halide VX3, a silicon halide SiX4, a halide niobium NbX5, a tantalum halide TaX5, a tungsten halide WX5, a bismuth BiX3 halide, borohydrides, chloroborates and mixtures thereof, X being, as above, an atom of halogen such as a bromine atom, a chlorine atom, a fluorine atom and an iodine atom. Preferably, the Lewis acid is (AIC13) or (GaCl3).
    [0004] When the strontium salt is Sr strontium tetrachloroaluminate (AIC14) 2, it may be prepared by reaction of strontium chloride SrCl 2 with AlCl 3 aluminum chloride. The strontium salt is present in the electrolyte at a concentration greater than 0.85 mol.L-1.
    [0005] More specifically, the strontium salt may be present at a concentration of from 0.85 mol.L-1 to 4 mol.L-1, preferably from 0.975 mol.L-1 to 3 mol.L-1, more preferably ranging from 1.15 mol.L-1 to 3 mol.L-1 and, even more preferably, ranging from 1.325 mol.L-1 to 2 mol.L-1. Finally, even more specifically, the strontium salt may be present at a concentration of 1.5 ± 0.1 mol.L-1. In addition to the presence of a solvent and a salt as defined above, the electrolyte may comprise one or more additives chosen, for example, to limit the self-discharge of batteries and landfill corrosion. This and these additives may be chosen from hydrofluoric acid (HF), SO.sub.2, salts such as GaCl.sub.3, BiCl.sub.3, BCI.sub.3, GaCl.sub.3, InCl.sub.3, VCI.sub.3, SiCl.sub.4, NbCl.sub.5, TaCl.sub.5, PCI.sub.5 and WCI.sub.6. This and these additives may be present in a content ranging from 0 to 50% of the concentration of the strontium salt. The batteries of the invention can be developed according to different technologies and, in particular, according to two cylindrical battery technologies, which are so-called concentric electrode structure cells and so-called spiral electrode structure cells, these cells being able to be different formats (such as AAA, AA, C, D or DD formats). For the cells of structure called concentric electrodes, they comprise, conventionally, as illustrated in Figure 2 attached in the appendix: - the positive electrode 11 placed in the center in the form of a carbon matrix and a support grid, the matrix being intended to accommodate the catholyte 12, namely the solvent, the electrolytic salt or salts and optionally the additives, the solvent also ensuring the role of active material of the positive electrode and the matrix 5 being intended, also, to recover reaction products; the negative electrode 13 disposed concentrically with respect to the positive electrode; between the positive electrode and the negative electrode, an annular separator and a separator in the form of a disk 17; A receptacle of the assembly in the form of a bucket 19, which also forms the negative pole of the stack; -a glass-metal crossing 21 welded to the bucket; a pin 23 positioned in the upper part of the battery at the glass-to-metal crossing, this pin constituting the positive pole of the battery, this pin being connected to the positive electrode via a positive connection 25. For batteries of AA format, the anode has, generally, a thickness between 0.3 and 1.5 mm and more specifically between 0.5 and 1 mm and the cathode has, generally, a thickness between 0.3 and 2 mm and, more specifically, between 0.5 and 1.5 mm. Nickel connections are generally used to provide the current collection. These connections are welded to the bucket for the negative electrode and to the pin of the glass-to-metal bushing for the positive pole. The separators must be neutral, insulating and chemically stable in the electrolyte used. They may be fiberglass with thicknesses ranging from 0.1 to 500 μm and, more specifically, from 0.1 to 300 μm.
    [0006] Depending on the arrangements, the positive electrode and the negative electrode may be inverted with respect to the configuration set forth above. These batteries are generally used for "energy" type applications, in which the currents are rather weak. The surface of the electrodes and, mainly that of the anode, is smaller which limits the corrosion in discharge.
    [0007] For piles of so-called spiral electrode structure, they conventionally comprise two rectangular flat electrodes whose width must be compatible with the height of the bucket and having a length configured so that, when wound on themselves, they constitute a cylinder whose diameter allows its introduction into the bucket for accommodating these electrodes. Such a stack is illustrated in FIG. 3 appended and comprises the following elements: the positive electrode 27 being in the form of a carbon matrix and a support grid, the matrix being intended to accommodate the catholite 28, at 10 namely the solvent, the electrolyte salt or salts and optionally the additives, the solvent also ensuring the role of active material of the positive electrode and the matrix being also intended to recover the reaction products; the negative electrode 29 wound around the positive electrode; between the positive electrode and the negative electrode, a spiral separator 31 and a separator in the form of a disk 33; a receptacle of the assembly in the form of a bucket 35, which also forms the negative pole of the battery; -a glass-metal crossing 37 welded to the bucket; a pin 39 positioned in the upper part of the stack at the glass-to-metal crossing, this pin constituting the positive pole of the battery, this pin being connected to the positive electrode via a positive connection 41. These cells are rather used for applications of "power" type, in which the currents are rather high, the surface of the electrodes being more important.
    [0008] Regardless of the geometry of the stack, the receptacle of the bucket assembly is preferably made of steel and seals the stack. Exposure of a larger anode surface to thionyl chloride can make these cells more susceptible to corrosion in storage and discharge. These cells may, for example, be used in pulsed discharge discharge profiles with large periodic power currents.
    [0009] As mentioned above, the cells of the invention find their application in all the fields requiring the production of electrical energy, in contexts where the temperature is high (in particular, temperatures higher than 200.degree. C.). This is particularly the case in the prospecting and exploitation of oil or in drilling for the use of geothermal energy. In these fields, the batteries of the invention can thus be used for the electrical power supply of measurement systems, which already include electronic components allowing operation at such temperatures. The invention will now be described with reference to the particular embodiments defined below and with reference to the accompanying figures. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a diagram illustrating the operating principle of a Li / SOCl2 cell.
    [0010] FIG. 2 is a sectional view of a so-called concentric electrode structure stack according to the invention. Figure 3 is a sectional view of a stack of so-called spiral electrode structure according to the invention. FIG. 4 is a discharge curve, that is to say a curve illustrating the evolution of the battery voltage U (in mV) as a function of time t (in hours) at constant current (17 mA) and at 210 ° C. with a battery comprising an electrolyte according to the invention (curve a), and with a battery comprising an electrolyte not according to the invention comprising a Sr (AIC14) 2 salt at 0.8 M (curve b) . FIG. 5 is a pulsed current discharge curve at 210 ° C with the following periodic power pulses: 9 sec / 5 mA-1 sec / 60 mA obtained with a battery according to the invention defined in Example 1 FIG. 6 is a constant current discharge curve (4 mA) and at 250 ° C. with a battery comprising an electrolyte according to the invention defined in example 1.
    [0011] FIG. 7 is a constant current discharge curve (4 mA) at 20 ° C. with a battery according to the invention defined in example 1. FIG. 8 is a constant current discharge curve (17 mA ) at 20 ° C with a battery according to the invention defined in Example 1.
    [0012] FIG. 9 is a discharge curve illustrating the evolution of the battery voltage U (in mV) as a function of time (in hours) at constant current (17 mA) and at 250 ° C. with a battery comprising a compliant electrolyte to the invention as defined in Example 2. Fig. 10 is a pulse discharge curve at 210 ° C with the following periodic power pulses: 9 sec / 5 mA - 1 sec / 60 mA with the battery compliant DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS EXAMPLE 1 The purpose of this example is to demonstrate the performance of batteries according to the invention over a wide range of temperatures, and particularly at high temperatures. high, and especially at temperatures above 200 ° C (and more specifically at 210 ° C and 250 ° C in this example). The tested cells are of so-called concentric electrode structure, as illustrated in FIG. 2 attached in the appendix. In a first test, the discharge curve, that is to say the curve illustrating the evolution of the battery voltage U (in mV) as a function of time (in hours) at constant current (17 mA), is determined. ) and at 210 ° C with a battery comprising an electrolyte according to the invention, namely 1.5 M of SrCl2 and 3M of AlCl3 (ie 1.5 M of Sr (AIC14) 2) in thionyl chloride SOCl2 and with a battery comprising an electrolyte not according to the invention comprising a 0.8M Sr (AIC14) 2 salt in thionyl chloride. This discharge curve is shown in FIG. 4 with, respectively, the curve a) for the cell according to the invention and curve b) for the cell not in accordance with the invention).
    [0013] For the battery according to the invention, it is observed that the discharge voltage remains greater than 2 V for more than 10 hours, whereas, for the battery not according to the invention, there is a very significant decrease of the voltage from the first hours and, in particular, a voltage already below 2 V after 4 hours of use. This attests to the efficiency of the batteries according to the invention at high temperatures. In a second test, the pulsed current discharge curve at 210 ° C. was determined with the following periodic pulses: 9 sec / 5 mA-1 sec / 60 mA with the battery according to the invention mentioned above, this curve is shown in Figure 5. The pulse voltage remains greater than 2 V for 9 hours, which validates the use of this type of battery for a pulsed application. It should be noted that the current voltages of 5 mA are high and higher than 3 V.
    [0014] In a third test, the constant current discharge curve (4 mA) and at 250 ° C are determined with a battery comprising an electrolyte according to the invention, this curve being shown in FIG. the discharge voltage remains above 2 V for more than 48 hours, which is very interesting at such a temperature.
    [0015] The composition of the electrolyte maintains a high voltage and provides a discharge profile at 250 ° C, characteristic of the liquid cathode primary battery technology. In a fourth test and in a fifth test, the constant-current discharge curve (4 mA) at 20 ° C. with a battery according to the invention is determined respectively, this curve being illustrated in FIG. 7; the constant-current discharge curve (17 mA) at 20 ° C. with a battery in accordance with the invention, this curve being illustrated in FIG. 8. At low current, the voltage remains greater than 2 V for more than 160 hours and at high current, the voltage remains above 2 V for more than 12 hours.
    [0016] This testifies to the possibility of using the batteries of the invention both at room temperature and at elevated temperature, as demonstrated with the previous tests.
    [0017] EXAMPLE 2 The purpose of this example is to demonstrate the performance of batteries according to the invention at elevated temperatures, and particularly at temperatures above 200 ° C (and more specifically at 210 ° C and 250 ° C in this example). example). The tested cells are of so-called spiral electrode structure, as illustrated in FIG. 3 attached in the appendix. In a first test, the discharge curve, that is to say the curve illustrating the evolution of the battery voltage U (in mV) as a function of time (in hours) at constant current (17 mA), is determined. ) and at 250 ° C with a battery comprising an electrolyte according to the invention, namely 1.5 M of SrCl2 and 3M of AlCl3 (or 1.5 M of Sr (AIC14) 2) in thionyl chloride SOCl2 , this curve being shown in FIG. 9. It is observed that the discharge voltage remains greater than 2 V for more than 10 hours. In a second test, the pulsed discharge curve at 210 ° C. was determined with the following periodic pulses: 9 sec / 5 mA-1 sec / 60 mA with the battery according to the invention mentioned above, this curve is shown in Figure 10. The pulse voltage is higher than when using concentric batteries, which validates the use of this type of battery for a pulsed application. Since the surface area of the electrodes is larger, the voltages are higher (lower current densities). Spiral electrode batteries are therefore more suitable for applications with a power requirement (ie for strong currents).
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. A liquid cathode battery comprising: a calcium anode; an electrolyte comprising a sulfur and / or phosphorus oxidizing solvent and at least one salt; a cathode comprising, as active material, a compound identical to the aforementioned oxidizing solvent; characterized in that the salt is a strontium salt present at a concentration greater than 0.85 mol.L-1.
    [0002]
    The liquid cathode battery of claim 1, wherein the cathode comprises a porous matrix of a carbonaceous material.
    [0003]
    The liquid cathode cell of claim 2, wherein the carbonaceous material is selected from carbon blacks, acetylene blacks, graphite, carbon fibers, and mixtures thereof.
    [0004]
    The liquid cathode battery according to claim 2 or 3, wherein the porous matrix is associated with a current collector substrate, which substrate is made of a metallic material.
    [0005]
    5. A liquid cathode cell according to any one of the preceding claims, wherein the oxidizing solvent is a sulfur-containing solvent, comprising one or more chlorine atoms, a non-chlorinated sulfur solvent or a phosphorus and optionally sulfur containing solvent comprising one or more atoms. chlorine.
    [0006]
    The liquid cathode battery according to claim 5, wherein the sulfur-containing solvent comprising one or more chlorine atoms is selected from thionyl chloride (SOCl2), sulfuryl chloride (SO2C12), disulfide dichloride (S2Cl2). ), sulfur dichloride (SCI2).
    [0007]
    The liquid cathode cell of claim 5, wherein the non-chlorinated sulfur solvent is sulfur dioxide.
    [0008]
    The liquid cathode cell of claim 5, wherein the phosphorus and optionally sulfur containing solvent comprising one or more chlorine atoms is selected from phosphoryl trichloride (POCl 3), thiophosphoryl trichloride (PSCl 3).
    [0009]
    The liquid cathode battery according to any of claims 1 to 6, wherein the oxidizing solvent is thionyl chloride (SOCl2). 15
    [0010]
    10. A liquid cathode cell according to any one of the preceding claims, wherein the strontium salt is a salt comprising a strontium cation SR 'associated with a halogen anion based on a member selected from aluminum, gallium, boron, indium, vanadium, silicon, niobium, tantalum, tungsten, bismuth. 20
    [0011]
    The liquid cathode cell of claim 10, wherein the halogen anion is chlorine-based.
    [0012]
    The liquid cathode cell according to any one of the preceding claims, wherein the strontium salt is the strontium Sr (AlC14) 2 tetrachloroaluminate salt.
    [0013]
    The liquid cathode cell according to any one of the preceding claims, wherein the strontium salt results from the in situ reaction of a Lewis acid and a Lewis base. 3032559 17
    [0014]
    14. A liquid cathode cell according to any one of the preceding claims, wherein the electrolyte comprises one or more additives selected from hydrofluoric acid (HF), SO2, salts such as GaCl3, BiCl3, BCl3, GaCl3, InCl3. , VCI3, SiCI4, NbCl5, TaCl5, PCI5 and WCI6.
    [0015]
    15. The liquid cathode battery as claimed in claim 1, which is a so-called concentric electrode structure stack or a so-called spiral electrode structure cell. 5 10
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    申请号 | 申请日 | 专利标题
    FR1551061A|FR3032559B1|2015-02-10|2015-02-10|SPECIFIC LIQUID CATHODE BATTERY THAT CAN OPERATE AT HIGH TEMPERATURES|FR1551061A| FR3032559B1|2015-02-10|2015-02-10|SPECIFIC LIQUID CATHODE BATTERY THAT CAN OPERATE AT HIGH TEMPERATURES|
    EP16703801.7A| EP3257095A1|2015-02-10|2016-02-10|Specific liquid cathode cell which can operate at high temperatures|
    US15/548,162| US20180026263A1|2015-02-10|2016-02-10|Battery with a specific liquid cathode which may operate at high temperatures|
    PCT/EP2016/052851| WO2016128482A1|2015-02-10|2016-02-10|Specific liquid cathode cell which can operate at high temperatures|
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