• 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:
    An electrochemical device (1), configured for storing electrical energy, comprising: - a reactor (2), the reactor wall (2) being configured to form a first electrode (3), the reactor (2) being provided an electrolyte inlet (4) and an electrolyte outlet (5), - a central electrode (6) disposed in the center of the reactor (2), - additional electrodes Ex, with x an integer ranging from 1 to n, the additional electrodes Ex being tubular and arranged around the central electrode (6).
    公开号:FR3025055A1
    申请号:FR1457875
    申请日:2014-08-19
    公开日:2016-02-26
    发明作者:Michel Jehan；Jean-Paul Briffod
    申请人:Jomi Leman；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD OF THE INVENTION The invention relates to an electrochemical device for the storage of electricity and to the production of hydrogen. electrical energy and for the production of hydrogen and a process for the production of hydrogen. STATE OF THE ART The massive storage of electrical energy presents considerable challenges. It is indeed essential to have storage units that can operate in a very wide range of power and capacity while focusing on reduced volume aspects. A promising way to store such energies is the electrochemical route. Today, the most efficient and safe electrochemical technology is that of the electrolysis of non-ferrous metals in an aqueous medium and, more particularly, the electrolysis of metals that have a high energy content such as zinc or manganese. . In addition, the technology is simple and cheap: it would be interesting to be able to operate such electrolysis reversibly. The application WO 2011/015723 describes a process for simultaneous co-generation of electrical energy and hydrogen by a totally electrochemical route. The method comprises a phase of electricity storage by electrolysis of a solution of an electrolyzable metal and formation of an electrolyzable metal battery-hydrogen and, a phase of electricity recovery and generation of hydrogen by operation of said battery .
    [0002] However, in such devices, the volumes of the reactors are very important in order to be able to supply a large quantity of electrical energy.
    [0003] In addition, for applications of high power, the metal deposits are often inhomogeneous, which reduces the electrochemical performance of the devices, or even causes short-circuiting of the electrodes by formation of metal dendrites.
    [0004] OBJECT OF THE INVENTION The object of the invention is to overcome the drawbacks of the prior art and, in particular, to propose a device making it possible to store a large quantity of electrical energy. This object is tendered by an electrochemical device, configured for the storage of electrical energy, comprising: a reactor, the reactor wall being configured to form a first electrode, the reactor being provided with an electrolyte inlet and an electrolyte outlet, - a central electrode disposed at the center of the reactor, - additional electrodes Ex, with x an integer ranging from 1 to n, the additional electrodes Ex being tubular and arranged around the central electrode . The additional electrodes are preferably bipolar. This object is also aimed at by an electrical energy storage method using said electrochemical device.
    [0005] Other advantages and features will become more clearly apparent from the following description of particular embodiments of the invention given by way of nonlimiting example and represented in the accompanying drawings, in which: FIG. FIG. 1 is a diagrammatic view, in section, of a reactor of an electrochemical device, according to one embodiment of the invention; FIG. 2 schematically represents, in plan view, a stack of electrodes of a reactor of an electrochemical device, according to the invention, - Figure 3 shows a schematic view, and in section, a reactor of an electrochemical device, according to another embodiment of the invention, - Figure 4 shows schematically. in plan view, an electrochemical device comprising a plurality of reactors, according to another embodiment of the invention; FIG. orelectrical expansion of two reactors, according to one embodiment of the invention.
    [0006] DESCRIPTION OF A PREFERRED EMBODIMENT OF THE INVENTION The invention relates to an electrochemical device for the storage of electrical energy in a direct and reversible manner.
    [0007] As shown in FIG. 1, the reversible electrochemical device 1, configured for the storage of electrical energy and for the production of hydrogen, comprises: a reactor 2, the reactor wall forming, advantageously, a reactor 1, first electrode 3, 3025055 4 reactor 2 being provided with an electrolyte inlet 4 and an electrolyte outlet 5, - a central electrode 6 disposed in the center of the reactor 2, the central electrode 6 being substantially parallel to the wall of the reactor 2, 5 - additional electrodes Ex, with x an integer ranging from 1 to n, the additional electrodes Ex being tubular and arranged around the central electrode 6. The central electrode 6 is preferably tubular. Tubular means that the electrode has a closed section preferably of cylindrical or ovoid shape. Advantageously, the electrode is hollow so as to allow the passage of the electrolyte. In one mode of operation, the central electrode 6 forms the anode of the electrochemical device. The central electrode 6 is then connected to a positive terminal of a DC power supply. The central electrode 6 is advantageously supported by the cover 7 of the reactor to facilitate the production of a robust device and simple to implement.
    [0008] In a particular case, the cover 7 is electrically conductive, it is then advantageous to electrically connect the cover 7 with the positive terminal of the DC power supply to bias the central electrode which is immersed in the electrolyte.
    [0009] The central electrode 6 is, for example, formed by an electrically conductive tube. Preferably, it is a metal tube. The metal tube may be coated with a coating on its outer diameter to promote electrochemical reactions and its resistance to chemical and gaseous attack.
    [0010] The central electrode 6 is advantageously made of an oxygen-resistant material in acidic medium. It, for example, coated with 3025055 titanium nitride on its surface, steel coated electrically conductive ceramics. This conductive ceramic is non-oxide. As shown in FIGS. 1 and 2, the additional electrodes Ex are, advantageously, tubular. They surround the central electrode 6. They are advantageously of increasing cross sections and symmetrical with respect to the central electrode 6. Preferably, the additional electrodes Ex are concentric. Concentric means that the electrodes are concentric or substantially lo concentric. Advantageously, the center of the additional electrodes Ex corresponds to the center of the central electrode 6. The additional electrodes Ex are nested one inside the other in the manner of "Russian dolls". Advantageously, the additional electrodes and the central electrode 6 are in the form of tubes. The electrode E1 is the additional electrode closest to the central electrode 6. This is the electrode proximal to the central electrode 6. The electrode En is the additional electrode furthest from the central electrode 6. This is the electrode distal to the central electrode 6.
    [0011] FIG. 1 represents, for example, a reactor comprising three additional concentric electrodes E1, E2 and E3 arranged around the central electrode. The distal electrode is the electrode E3. FIG. 2 represents, in top view, additional electrodes Ex with x = 4. The distal electrode is the electrode E4.
    [0012] The electrochemical potential of the additional electrodes Ex is said to be floating, that is to say that the total potential difference brought by the electric generator between the electrode 6 and the electrode 3 supported by the tank is distributed naturally between each of the electrodes Ex.
    [0013] Preferably, the Ex electrodes have the same morphology, i.e. the shape of one of the electrodes is modified by homothety to form the other electrodes. This configuration allows a fixed distance between two electrodes and therefore a better distribution of potentials and chemical reactions.
    [0014] Advantageously, a tubular configuration makes it possible to limit the deformation of the electrodes during the electrolysis. It is thus possible to substantially reduce the thickness of the electrodes relative to electrodes configured in flat structures which deform very strongly. The use of concentric, rather than planar tubular electrodes provides a more compact stack with an improved exchange surface. This assembly of electrodes makes it possible to obtain large reaction surfaces in an extremely small space requirement. The volume of the reactor 2 can be considerably reduced. Such devices make it possible to store larger amounts of energy than a device with planar electrodes for the same reactor volume. The number of additional electrodes depends on the desired electrical power. The total number of floating electric potential electrodes supported in the vessel is an odd number. The additional electrodes Ex have different heights. Preferably, the additional electrodes Ex have a height 1-1x, the height Hx of the electrodes being decreasing from the proximal electrode E1 to the distal electrode En. The height of each of the electrodes is defined by the formula: Hx = Do.H1 / (Do + 2.Pn) with H1 the height of the electrode x 30 Do the diameter of the central electrode in mm, H1 the height of the proximal electrode in mm 3025055 7 P the distance between two successive electrodes, the pitch between two successive electrodes, n the number of additional electrodes.
    [0015] Advantageously, the active reaction surface remains homogeneous from one pair to the other, from the center of the reactor, to the outer body, the surface varying in the ratio of the perimeters of the concentric elements whose height is calculated according to the objective of an iso-density of current.
    [0016] The pitch P, the distance between two successive electrodes, is advantageously between 0.2 cm and 4 cm. Preferably, the distance between the electrodes is between 0.5 cm and 1.5 cm, which makes it possible to reduce the ohmic losses considerably.
    [0017] Preferably, the architecture of the reactor is configured so that the additional electrodes Ex are bipolar. Bipolar means that the electrodes can play both the role of anode and cathode. The bipolar electrode has two faces: an anode face and a cathode face. During the electroplating step, the metal is deposited on the cathodic face and the native oxygen is formed on the anodic side. These particular electrodes are advantageously designed in materials adapted to these electrochemical conditions, and in particular to bipolarity. The electrodes are, for example, lead, nickel, titanium with, advantageously, for each of said materials electrically conductive coatings such as non-oxide ceramics. The electrodes may also be mixed bipolar electrodes made of lead and lead oxide, or lead alloy.
    [0018] Preferably, the storage of the electrical energy is carried out on mixed bipolar electrodes in lead and lead oxide, thus forming a battery, in a cylindrical and concentric configuration. These electrodes 3025055 8 allow the storage of energy in a very small volume having a large exchange surface. Bipolar electrodes allow full reversal of polarity and counter-electrode operation in the etching phase when the polarities reverse when the reactor is used as a hydrogen generator. The hydrogen is extracted under pressure through the lid by the gas outlet or collector 8.
    [0019] Preferably, at least one of the faces of the additional electrodes is coated with conductive ceramics. Ceramics are advantageously non-oxides. It may be silicon carbide (SiC), titanium carbide (TiC), silicon nitride (Si3N4), titanium nitride (TiN), etc.
    [0020] Advantageously, the set of additional bipolar Ex electrodes thus forms a compact stack of electrochemical surfaces vis-à-vis each other, one side of which behaves anode and the other face of cathode. The additional electrodes Ex are electrically isolated from each other. They are also electrically insulated from the wall of the reactor 2 which forms the cathode, and from the central electrode 6, which forms the anode. The potential between each electrode, called "floating potential" naturally equilibrates in the electrolyte bath flowing between the electrodes. This potential depends on the potential difference applied between the vessel and the reactor cover, as well as the number of additional electrodes E. The reactor 2 is, for example, a vessel. The tank is made of an electrically conductive material. The reactor is, advantageously, configured so that the electrolyte circulates from the center of the reactor 30 towards its periphery following the circuit imposed by the electrodes E. In this way, it is easier to control the reactions to the reactor. inside the reactor.
    [0021] Advantageously, the material forming the tank, as well as the thickness of the material, will be chosen by those skilled in the art so as to have mechanical properties enabling it to withstand hydrogen pressure and corrosion. The tank is, for example, aluminum. It is advantageously cathodically protected. Advantageously, the center of the tank corresponds to the center of the central electrode 6 and also to the center of the additional electrodes E. All these elements are concentric. The reactor 2 is, preferably, a closed reactor in which the electrolyte circulates. The reactor is formed of a wall, a bottom and a lid. The wall is a side wall. It is, preferentially, circular.
    [0022] The reactor wall advantageously forms the first electrode 3. According to another embodiment, the first electrode could be formed by another tubular electrode disposed between the additional electrode En and the reactor wall. The reactor wall advantageously forms a first electrode. It forms the cathode of the device. It is connected to the negative pole of the DC power supply. The reactor is closed, in its upper part by a cover 7. Advantageously, the cover 7 is in the form of a truncated cone to withstand the gas pressure generated inside the reactor. The lid 7 comprises, for example, a clamping flange at its periphery and a seal serving both to maintain the pressure inside the tank and, at the same time, electrical insulation between the tank at the negative potential and the lid 7 to the positive potential of the external electrical generator.
    [0023] The cover 7 serves as a mechanical support for the central electrode 6 which acts as an anode. The cover 7 is electrically connected to the anode and is brought to the potential of the positive terminal of the external power supply.
    [0024] The gases released during the operating phases are collected via the upper part of the reactor 2, which is provided with a gas outlet 8. Flow and liquid flow sensors as well as sensors measuring the electrical conditions of the device during the different process steps are integrated into the electrochemical device. The device may, in addition, comprise a computer for regulating the liquid flow rate as a function of the gas flow rate.
    [0025] According to a preferred embodiment, the bottom 9 of the reactor is electrically insulating. For example, and as shown in FIG. 1, an electrically insulating plate 10 is deposited on the bottom 9 of the reactor 2 and prevents electrical contact between the bottom 9 of the reactor 2 and the electrodes 3. Preferably, the electrically insulating plate 10 allows to ensure both the electrical insulation of the electrodes inside the reactor but also to play the role of mechanical support. The concentricity of the electrodes is by their interlocking in circular grooves machined in this electrical insulator. The grooves are machined to define the pitch P. According to a preferred embodiment, the electrolyte inlet 4 of the reactor 20 is disposed, in the upper part of the central electrode, at the top of the central electrode 6. For example, the electrolyte is propelled through the cover into the central electrode by a positive displacement pump, which enables the flow rate and the pressure to be adjusted.
    [0026] The electrolyte outlet 5 is disposed in the lower part of the reactor 2, between the electrode En and the reactor wall. In the case where the bottom 9 of the tank is electrically insulating, the central electrode 6 and the additional electrodes Ex with x an even integer are separated from the bottom 9 of the reactor 2, by a void space. Additional electrodes 3025055 11 Ex with x an odd integer are in contact with the bottom 9 of the reactor 2. In the case where the bottom 9 of the tank is covered with an electrically insulating plate 10, the additional electrodes Ex with x an integer are separated from the electrically insulating plate 10 by a void space, and the additional electrodes Ex with x an odd integer are in contact with the bottom 9 of the reactor 2 the electrically insulating plate 10. A flow path of the The electrolyte is thus formed, the path going from the electrolyte inlet 4 to the electrolyte outlet 5, alternately passing at the level of the upper part or at the level of the lower part of the additional electrodes E. The path of the electrolyte electrolyte is schematically represented by arrows in FIG.
    [0027] The electrolyte flows, firstly, into the tube of the central electrode 6, then it goes up along the additional electrode El. By overflow, it passes over the additional electrode E1 for reach the second reaction interface.
    [0028] The electrolyte then passes through the calibrated holes at the foot of the electrode E2. The electrolyte thus flows symmetrically from the central electrode to the electrode En, where after a last overflow, it is discharged from the tank through an orifice, forming the electrolyte outlet 5, arranged in the foot of the tank.
    [0029] In this embodiment, the circulation of the electrolyte is natural and safe. This architecture makes it possible to obtain an excellent circulation of the electrolyte flows, its permanent renewal at the right of each electrode by using the central electrode 6, as a means of introducing the electrolyte into the reactor through the center of the reactor. this. The decreasing height of the electrodes from the proximal electrode E1, the most 3025055 12 close to the central electrode, towards the distal electrode En, the furthest away from the central electrode, ensures the overflow of the electrolyte and makes it possible to control the current densities of the electrode pairs that must be constant.
    [0030] The circulation of the inter-electrode fluids is simplified because it is directed symmetrically from the reactor center to the outside of the reactor, by a single supply. Such a geometry, entirely symmetrical, allows to deliver a relevant flow of electrical currents from one electrode to another and to eliminate the leakage currents. The control of the circulation of electric currents, associated with a decrease of the turbulences, results in a better homogeneity of the metallic deposits.
    [0031] Advantageously, the heat losses are reduced and well distributed. According to another preferred embodiment, and as shown in FIG. 3, the upper level of the additional electrodes Ex is at the same height. The level of the electrodes can be equalized, thanks to shims placed at the foot of each electrode. The wedges make it possible to maintain a space between the bottom of the reactor and the additional electrodes. A holding system may also be disposed at the top of the electrodes. The shims and the holding system, not shown in FIG. 3, are electrically insulating. This configuration is particularly used when the reactor 2 comprises lead electrodes, in the case of direct storage of electricity, and without gas evolution (reactor working at atmospheric pressure).
    [0032] Advantageously, in this embodiment, the bottom of the reactor 9 does not need to be insulating.
    [0033] The arrival of the electrolyte 4 is disposed in the upper part of the reactor 2, and the electrolyte outlet 5 is disposed in the lower part of the reactor 2. The electrolyte outlet 5 may be formed of one or several orifices, arranged at the bottom 9 of the reactor 2.
    [0034] Only the arrival of electrolyte 4 in the tank has been shown. The electrochemical device 1 comprises an injector 11, connected to the electrolyte inlet, and configured to inject the electrolyte between each additional electrode. The electrolyte then flows parallel between each electrode. The flow of the electrolyte is represented by arrows in FIG.
    [0035] The level of electrolyte rises gradually in the reactor, gradually putting the electrodes of the various couples in contact with each other via said electrolyte. Preferably, and as shown in FIG. 4, the reactor 2 is placed in a cooling tank 12 to allow the accumulated heat to be evacuated in the body of the tank 2, and thus to avoid problems of overheating of the device electrochemical. Advantageously, in the event of hydrogen leakage, for example, the hydrogen is distributed in the water of the cooling tank where it is, advantageously, immediately dissolved. The electrochemical device, with its assembly of bipolar electrodes, has, during its operation, an ideal distribution of the electric currents passing from a bipolar electrode to another electrode while ensuring a precise and controlled gravity flow of the electrolyte flows. of the chemical solution containing the metal to be deposited. The assembly of the electrodes within the electrochemical device makes it possible to obtain a better compactness of the active surfaces, an electrochemical compression of the product gas, operation at selected temperatures at room temperature with very improved heat exchange coefficients. and the partial and direct recovery of the electrical energies induced in chemical dissolution reactions. The morphology of the electrodes, the original electrical connections by the reactor body with complementary internal stacking of bipolar electrodes having an electric potential floating between the main cathode, the reactor body and the central anode supported by the reactor cover allows obtain a very compact and concentric assembly having a high active surface density in a reduced volume.
    [0036] The reversible process for storing electrical energy or for producing hydrogen comprises the following successive steps: - supplying an electrochemical device 1 as described above; - introducing an electrolyte into the electrochemical device 1, the electrolyte 15 containing metal ions, - electrically connecting the first electrode 3 to the negative terminal of a power supply and the central electrode 6 to the positive terminal of a power supply, - supplying electrical energy to reduce the metal ions on the 20 electrodes, so as to form an electrolysable-dihydrogen metal battery. The electrolyte contains metal ions. It may be, for example, zinc, manganese or nickel, or cadnium.
    [0037] The first electrochemical step, i.e. energy storage, is performed by electroplating the metal in solution on the electrodes of the electrochemical device 1. The storage of the electrical energy is in the form of a metal deposit.
    [0038] When electroplating the metal, electrical energy is consumed. The electrolyte, also called liquor, can be added permanently with water, containing sulphates of a metal.
    [0039] During the electrodeposition phase of the metal on the cathodes, i.e. on the reactor wall and on the cathode faces of the bipolar electrodes nested one inside the other, the oxygen is released at the anodes. The oxygen is extracted from the reactor through an orifice disposed in the upper part of the lid. Advantageously, the oxygen is removed continuously.
    [0040] During electrodeposition of the metal, the metal content of the electrolyte evolves, gradually decreasing. For example, in the case of a zinc sulfate electrolyte, the mass concentration of the metal electrolyte decreases from 150g / L, at the beginning of the electroplating phase, to less than 50g / L, at the end of the electroplating phase. At the same time, the electrolyte acidifies as it goes along. Preferably, at the beginning of the electroplating phase, the mass concentration of metal is between 100 g / l and 200 g / l. Even more preferentially, it is of the order of 150 g / l.
    [0041] Preferably, the device 1 comprises an electrolyte reservoir connected to the electrolyte inlet 4 and to the electrolyte outlet 5 of the reactor 2, so as to form a closed circuit. The electrolyte, used to form the electrolyzable-dihydrogen metal cell, is reused for the operating phase of said cell. During the electroplating phase, the electrolyte is stored progressively in the storage tank. The tank then serves as a supply reserve for the phase of production of electrical energy.
    [0042] After the electroplating phase, the electrolyte is advantageously removed from the reactor 2. By this emptying of the electrolyte, there is no longer any current flow and the circuit is open. The metal deposition produced is stable when the electrolyte is emptied from the tank and is no longer in contact with said deposited metal. The deposit is preserved for a long time without oxidizing, inherently retaining the electrical energy that it consumed during its electroplating. The method comprises, after forming the electrolysable dihydrogen metal cell, an operating phase of said cell, the operating phase comprising dissolving the previously deposited metal so as to produce electrical energy and dihydrogen. The electrolyte, used to form the electrolyzable-dihydrogen metal cell, is reused for the operating phase of said cell.
    [0043] According to a preferred embodiment, after formation of the electrolysable-dihydrogen metal cell, the electrolyte is emptied from the reactor 2. This allows the electrodes to be stored for long periods of time. Advantageously, the electrolyte is always emptied from the reactor in the intermediate phases and in the rest phase of the equipment, when the equipment is out of current. The electrolyte is reintroduced during the operating phase of said cell for the production of dihydrogen. During the operating phase of the electrolysable-dihydrogen metal battery, i.e. during the dissolution of the metal, the electrical energy is recovered. The first electrode 3 and the central electrode 6 are connected to an energy recovery system. The reactor provides hydrogen under pressure. The pressure is, for example, of the order of 80 bars.
    [0044] The dihydrogen, formed during the operating phase of the electrolyzable-dihydrogen metal cell, is extracted under pressure by the gas outlet 8.
    [0045] During the controlled dissolution of said metal deposited on the electrodes in the reactor used for the deposition, the electrolyte circulates, advantageously, in a controlled manner between the electrodes. The electrolyte circulates by gravity controlled overflow. The electrolyte was formed in the previous operation, circulating in a closed loop and whose acid content has evolved and will no longer have the same stoichiometry compared to the initial sulphate content, this dissolution producing on the counter-electrode connected Electrically a release of hydrogen, the reactor having become an electric generator 10 by the effect of batteries. Advantageously, the electrolyte is introduced into the reactor, from the storage tank, at a corresponding pressure by a pump. The electrochemical device may comprise a valve calibrated specifically, or regulated by an external automaton, to the required pressure. The valve adjusts the pressure on the outlet 5 of the tank. The acid content is at the beginning of the etching between 50g / L and 200g / L.
    [0046] As the chemical etching of the metal progresses, the metal is redissolved in the electrolyte. In the case of zinc, the zinc sulphate solution is regenerated for a new future use, the electrolyte flowing in a closed loop.
    [0047] The controlled circulation of the electrolyte allows, according to the configuration chosen, either the direct storage of the electrical energy, or the direct transformation of the electrical energy into hydrogen under pressure, during a second electrochemical step. The reactor behaves as a cathode during the storage phase, and it also serves as a gaseous generator under pressure during the production phase of electrical energy and hydrogen.
    [0048] According to a preferred embodiment, several reactors are electrically coupled. The reactors can be coupled in series and in parallel. Preferably, the device comprises at least one second reactor, the two reactors being connected in series, the reactors being electrically connected. The two reactors are in fluid communication: the second reactor is disposed between the first reactor and the electrolyte reservoir, the electrolyte outlet of the first reactor being connected to the electrolyte inlet of the second reactor, and the outlet of the reactor. electrolyte of the second reactor being connected to the electrolyte reservoir. For example, and as shown in FIG. 4, seven reactors were connected in series in a cooling tank 12.
    [0049] The reactors are electrically symmetrical. Each reactor comprises 19 internal electrodes, i.e. 20 electrochemical pairs. Each reactor can provide 60 volts. The electrodes are mixed lead and titanium electrodes coated with complex nitrides.
    [0050] Each set of electrodes has an active surface area of between 20 and 25 m 2 for an outside reactor diameter of less than 1 m. Each reactor is traversed by a current of 500 amperes. In the tests carried out, in the presence of zinc sulphate, and during the electroplating step, between 15 kg and 20 kg of zinc were deposited per reactor and 25 per hour under current. In the second step, in the hydrogen production configuration, a flow rate of 1000 to 1500 Nm3 / h (for cubic normo-meter per hour) of hydrogen was obtained.
    [0051] Cooling tank 12 allowed the seven reactors to be cooled to an operating temperature of between 30 ° C and 70 ° C.
    [0052] Advantageously, the electrical connections for the operation of the electrochemical device are very simple to put in place. The reactor is fed by a DC generator during the energy storage phase, and the reactor itself behaves as a controlled generator when it generates hydrogen. The central anode is firmly attached by its electrical connection to the cover, while the reactor body, forming the cathode, is connected to the negative terminal of the generator during electrodeposition of the metal. During the chemical attack, the reactor acts as an electric generator. It is then electrically connected to one or more energy recovery systems. FIG. 5 represents an electrochemical device comprising two electrically coupled reactors.
    [0053] This configuration makes it possible to use the electric generator effect by using the energy produced in the reactor in the electroplating phase of the metal, thanks to couplings with DC-DC BOOST converters. The couplings allow the reversal of the directions of the electric currents. The reactors are during a given period of electrical energy receiver.
    [0054] This is the case of the electroplating phase. They then produce oxygen. An external DC power supply provides the energy needed for electroplating. This direct current can also be pulsed. The reactors are then generators of electrical energy in the etching phase of the deposited metal. They then generate an electric current, 25 by stack effect. The current is used through the reversible electronic converter assembly. The method makes it possible to store available electrical energy, for example, during off-peak hours and to restore the stored electrical energy with a high efficiency, for example during peak hours, the return of electrical energy being accompanied by production. hydrogen.
    权利要求:
    Claims (20)
    [0001]
    REVENDICATIONS1. An electrochemical device (1), configured for storing electrical energy, and mass production of hydrogen comprising: - a reactor (2), the reactor wall (2) being configured to form a first electrode (3), the reactor (2) being provided with an electrolyte inlet (4) and an electrolyte outlet (5), - a central electrode (6) disposed at the center of the reactor (2), - additional electrodes Ex , with x an integer ranging from 1 to n, the additional electrodes Ex being tubular and arranged around the central electrode (6).
    [0002]
    2. Electrochemical device (1) according to claim 1, characterized in that the additional electrodes Ex are provided with an anode face and a cathode.
    [0003]
    3. Electrochemical device according to claim 2, characterized in that at least one of the faces of the additional electrodes is coated with conductive ceramics.
    [0004]
    4. Electrochemical device according to any one of claims 1 to 3, characterized in that the additional electrodes Ex have a height Hx, the height Hx of the electrodes being decreasing from the proximal electrode E1 to the distal electrode En.
    [0005]
    5. Electrochemical device (1) according to claim 4, characterized in that the height Hx of the electrodes is defined by Hx = Do.H1 / (Do + 2.Pn) with Hx the height of the electrode x 3025055 21 Do the diameter of the central electrode in mm, H1 the height of the proximal electrode in mm P the distance between two successive electrodes, n the number of additional electrodes E. 5
    [0006]
    6. Electrochemical device (1) according to any one of claims 1 to 5, characterized in that the bottom (9) of the reactor (2) is electrically insulating. 10
    [0007]
    7. Electrochemical device (1) according to any one of claims 1 to 6, characterized in that: - the arrival of the electrolyte (4) is disposed in the upper part of the central electrode (6), - the electrolyte outlet (5) is arranged in the lower part of the reactor (2), between the electrode En and the reactor wall (2), the central electrode (6) and the additional electrodes Ex with x an even integer are separated from the bottom of the reactor (2) by a space, - the additional electrodes Ex with an odd integer are in contact with the bottom of the reactor (2), so as to form a flow path of the reactor. electrolyte, the path from the electrolyte inlet (4) to the electrolyte outlet (5), alternately passing at the top of the Ex electrodes with x an odd integer and at the bottom Ex electrodes with x an even integer. 25
    [0008]
    8. Electrochemical device (1) according to any one of claims 1 to 6, characterized in that: - the arrival of the electrolyte (4) is disposed in the upper part of the reactor (2), 30 - the output the electrochemical device (1) comprises an injector (11) configured to inject the electrolyte between each additional electrode Ex, the additional electrodes Ex being separated, in the lower part of the reactor (2). from the bottom of the reactor (2) by a space.
    [0009]
    Electrochemical device (1) according to one of Claims 1 to 8, characterized in that the additional electrodes Ex are electrically isolated from one another and in that they are electrically isolated from the first electrode (3) and from the central electrode (6).
    [0010]
    10. Electrochemical device (1) according to any one of claims 1 to 9, characterized in that the reactor (2) is disposed in a cooling tank (12). 15
    [0011]
    Electrochemical device (1) according to any one of claims 1 to 10, characterized in that the device (1) comprises an electrolyte reservoir connected to the electrolyte inlet (4) and at the outlet of electrolyte (5) of the reactor (2) so as to form a closed circuit. 20
    [0012]
    12. Electrochemical device (1) according to any one of claims 1 to 11, characterized in that the device comprises at least a second reactor, the two reactors being connected in series, the reactors being electrically connected, and in that the second reactor is disposed between the first reactor and the electrolyte reservoir, the electrolyte outlet of the first reactor being connected to the electrolyte inlet of the second reactor, and the electrolyte outlet of the second reactor being connected to the reservoir; electrolyte.
    [0013]
    Electrochemical device (1) according to any of claims 1 to 12, characterized in that the first electrode (3) is electrically connected to the negative terminal of a power supply and that the first electrode (3) is electrically connected to the negative terminal of a power supply. central electrode (6) is connected to the positive terminal of the power supply.
    [0014]
    Electrochemical device (1) according to one of Claims 1 to 12, characterized in that the first electrode (3) and the central electrode (6) are connected to an energy recovery system.
    [0015]
    15. A method of storing electrical energy, comprising the following successive steps: - supplying an electrochemical device (1) according to any one of claims 1 to 14, - introducing an electrolyte into the electrochemical device (1), electrolyte containing metal ions, - electrically connecting the first electrode (3) to the negative terminal of a power supply and the center electrode (6) to the positive terminal of a power supply, - supplying energy electrode for reducing the metal ions on the electrodes of the electrochemical device (1), so as to form an electrolysable-dihydrogen metal battery. 20
    [0016]
    16. The method of claim 15, characterized in that the method comprises, after the formation of the electrolysable-dihydrogen metal battery, a phase of operation of said stack, the operating phase comprising the dissolution of the deposited metal so as to produce electrical energy and dihydrogen.
    [0017]
    17. The method of claim 16, characterized in that, during the dissolution of the metal, the first electrode (3) and the central electrode (6) are connected to an energy recovery system. 3025055 24
    [0018]
    18. Method according to one of claims 16 and 17, characterized in that the dihydrogen, formed during the operating phase of the electrolysable-dihydrogen metal battery, is extracted under pressure by the gas outlet (8). 5
    [0019]
    19. Method according to one of claims 15 and 18, characterized in that the electrolyte, used to form the electrolysable-dihydrogen metal battery, is reused for the operating phase of said battery.
    [0020]
    20. Process according to any one of claims 15 to 19, characterized in that, after formation of the electrolysable-dihydrogen metal cell, the electrolyte is emptied from the reactor (2). 15
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    同族专利:
    公开号 | 公开日
    CN107004929A|2017-08-01|
    JP2017532750A|2017-11-02|
    CA2958474A1|2016-02-25|
    KR20170100475A|2017-09-04|
    CN107004929B|2020-10-23|
    ZA201701907B|2018-05-30|
    JP6744306B2|2020-08-19|
    EP3183770A1|2017-06-28|
    WO2016027031A1|2016-02-25|
    US20170271706A1|2017-09-21|
    FR3025055B1|2016-08-26|
    AU2015305072A1|2017-03-09|
    EP3183770B1|2018-07-18|
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    CN107541747B|2016-06-27|2019-02-19|中国科学院金属研究所|A kind of energy storage device integrating optical electro-chemical water decomposes the design method of battery|
    FR3079529A1|2018-04-03|2019-10-04|Ergosup|ELECTROCHEMICAL PROCESS FOR THE PRODUCTION OF GASEOUS HYDROGEN UNDER PRESSURE BY ELECTROLYSIS AND BY DEPOLARIZATION|
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    CN109888352A|2019-02-20|2019-06-14|熵零技术逻辑工程院集团股份有限公司|A kind of chemical energy device for converting electric energy|
    法律状态:
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    2016-02-26| PLSC| Search report ready|Effective date: 20160226 |
    2016-08-17| PLFP| Fee payment|Year of fee payment: 3 |
    2017-07-12| PLFP| Fee payment|Year of fee payment: 4 |
    2018-08-27| PLFP| Fee payment|Year of fee payment: 5 |
    2019-08-29| PLFP| Fee payment|Year of fee payment: 6 |
    2020-08-28| PLFP| Fee payment|Year of fee payment: 7 |
    2021-08-30| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1457875A|FR3025055B1|2014-08-19|2014-08-19|ELECTROCHEMICAL DEVICE FOR STORING ELECTRIC ENERGY AND HYDROGEN PRODUCTION, AND PROCESS FOR PRODUCING HYDROGEN|FR1457875A| FR3025055B1|2014-08-19|2014-08-19|ELECTROCHEMICAL DEVICE FOR STORING ELECTRIC ENERGY AND HYDROGEN PRODUCTION, AND PROCESS FOR PRODUCING HYDROGEN|
    CN201580050991.7A| CN107004929B|2014-08-19|2015-08-17|Electrochemical device for storing electric energy and producing hydrogen and method for producing hydrogen|
    US15/505,385| US20170271706A1|2014-08-19|2015-08-17|Electrochemical device for storing electrical energy and producing hydrogen, and method for producing hydrogen|
    EP15759904.4A| EP3183770B1|2014-08-19|2015-08-17|Electrochemical device for storing electrical energy and producing hydrogen, and method for producing hydrogen|
    JP2017529152A| JP6744306B2|2014-08-19|2015-08-17|Electrochemical apparatus for storing electrical energy to produce hydrogen, and method for producing hydrogen|
    CA2958474A| CA2958474A1|2014-08-19|2015-08-17|Electrochemical device for storing electrical energy and producing hydrogen, and method for producing hydrogen|
    AU2015305072A| AU2015305072A1|2014-08-19|2015-08-17|Electrochemical device for storing electrical energy and producing hydrogen, and method for producing hydrogen|
    PCT/FR2015/052215| WO2016027031A1|2014-08-19|2015-08-17|Electrochemical device for storing electrical energy and producing hydrogen, and method for producing hydrogen|
    KR1020177007528A| KR20170100475A|2014-08-19|2015-08-17|Electrochemical device for storing electrical energy and producing hydrogen, and method for producing hydrogen|
    ZA2017/01907A| ZA201701907B|2014-08-19|2017-03-17|Electrochemical device for storing electrical energy and producing hydrogen, and method for producing hydrogen|
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