EP3516093A1

EP3516093A1 - System for high-temperature reversible electrolysis of water comprising a hydride tank coupled with the electrolyser

Info

Publication number: EP3516093A1
Application number: EP17780483.8A
Authority: EP
Inventors: Vincent Lacroix; Albin Chaise; Julie CREN; Magali Reytier; Guilhem Roux
Original assignee: Commissariat a lEnergie Atomique CEA; Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Current assignee: Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date: 2016-09-19
Filing date: 2017-09-18
Publication date: 2019-07-31
Also published as: US11542610B2; FR3056230A1; JP7446372B2; JP2019534940A; CA3037108A1; JP7170630B2; FR3056230B1; JP2022167936A; US20190245224A1; WO2018051041A1

Abstract

The invention relates mainly to a system (10) for high-temperature reversible electrolysis of water, characterised in that it includes: a high-temperature reversible electrolyser (11), configured to operate in SOEC (solid oxide electrolyser cell) mode to produce hydrogen and store electricity, and/or in SOFC (solid oxide fuel cell) mode to withdraw hydrogen and produce electricity; a hydride tank (12), thermally coupled with said reversible electrolyser, the system being configured to allow the recovery of heat released by the hydride tank during hydrogen absorption in order to produce pressurised steam intended for entering the reversible electrolyser in SOEC mode, and to allow the recovery of heat released by the one or more outgoing streams from the reversible electrolyser in SOFC mode so as to allow the desorption of hydrogen from the hydride tank.

Description

HIGH-TEMPERATURE REVERSIBLE WATER ELECTROLYSIS SYSTEM COMPRISING A HYDRIDE RESERVOIR COUPLED WITH THE ELECTROLYSER

DESCRIPTION TECHNICAL FIELD

The present invention relates to the general field of electrolysis of high temperature water (EHT), in particular the electrolysis of high temperature water vapor (EVHT), respectively designated by the English names "High Electrolysis Temperature (HTE) and High Temperature Steam Electrolysis (HTSE).

It also relates to the field of solid oxide fuel cells, usually designated by the acronym SOFC for "Solid Oxide Fuel Cells".

More specifically, the invention relates to the storage of electricity and its return, or destocking, through a reversible electrolysis of water, resulting in the production and / or consumption of hydrogen.

Thus, the invention provides a reversible electrolysis system for high temperature water comprising a reversible electrolyzer device and a hydride reservoir thermally coupled to this electrolyzer, and a reversible electrolysis method associated.

STATE OF THE PRIOR ART To perform the electrolysis of water, it is advantageous to produce it at a high temperature, typically between 600 and 950 ° C., since it is more advantageous to electrolyze steam than water. liquid (15%) and that part of the energy required for the reaction can be provided by the cheaper than electricity.

To implement the electrolysis of high temperature water (EHT), it is known to use a high temperature solid oxide electrolyser SOEC type (for "Solid Oxide Electrolyzer Cell" in English), consisting of a stack of elementary patterns each comprising a solid oxide electrolysis cell, consisting of three anode / electrolyte / cathode layers superimposed on each other, and plates interconnect in metal alloys, also called bipolar plates or interconnectors. A solid oxide fuel cell (SOFC) consists of the same type of stack of elementary patterns.

It should be noted that the interconnection devices, electrical and fluidic, also called interconnectors or interconnect plates, are the devices that provide the series connection from an electrical point of view of each electrochemical unit of elementary pattern in the stacking elemental patterns of high temperature solid oxide electrolysers (SOEC) or solid oxide fuel cells (SOFC), and in parallel fluidically, thus combining the production of each of the cells. The interconnectors thus provide power supply and collection functions and define gas circulation compartments for distribution and / or collection.

More precisely, the function of the interconnectors is to ensure both the passage of electric current and the circulation of gases in the vicinity of each cell (namely: injected water vapor, hydrogen and oxygen extracted for electrolysis EHT; and fuel whose injected hydrogen and extracted water for a SOFC cell), and to separate the anode and cathode compartments which are the gas flow compartments on the anode and cathode side respectively of the cells.

To carry out the electrolysis of water vapor at high temperature (EHT), water vapor (H ₂ 0) is injected into the cathode compartment. Under the effect of the electric current applied to the cell, the dissociation of the water molecules in vapor form is carried out at the interface between the hydrogen electrode (cathode) and the electrolyte: this dissociation produces dihydrogen gas ( H ₂ ) and oxygen ions (O ² ). The hydrogen (H ₂ ) is collected and discharged at the outlet of the hydrogen compartment. Oxygen ions (O ² ) migrate through the electrolyte and recombine into oxygen (0 ₂ ) at the interface between the electrolyte and the oxygen electrode (anode). A draining gas, such as air, can circulate at the anode and thus collect the oxygen generated in gaseous form at the anode.

To operate a solid oxide fuel cell (SOFC), air (oxygen) is injected into the cathode compartment of the cell and hydrogen in the anode compartment. The oxygen of the air will dissociate into 0 ^{2 ~} ions. These ions will migrate into the electrolyte from the cathode to the anode to oxidize hydrogen and form water with simultaneous generation of electricity. In SOFC cell, as in SOEC electrolysis, the water vapor is in the hydrogen compartment (H ₂ ). Only the polarity is reversed.

By way of illustration, Figure 1 shows a schematic view showing the operating principle of a high temperature solid oxide electrolyser (SOEC). Such an electrolyzer is an electrochemical device for producing hydrogen (and oxygen) under the effect of an electric current. In these electrolysers, the electrolysis of water at high temperature is carried out from steam. Thus, the function of such an electrolyzer is to transform the water vapor into hydrogen and oxygen according to the following electrochemical reaction:

2H ₂ 0 ^ 2H ₂ + 0 ₂ .

This reaction is carried out electrochemically in the cells of the electrolyser. As shown diagrammatically in FIG. 1, each elementary electrolysis cell 1 is formed of a cathode 2 and an anode 4 placed on either side of a solid electrolyte 3. The two electrodes (cathode and anode) 2 and 4 are electronic and / or ionic conductors, of porous material, and the electrolyte 3 is gas-tight, electronic insulator and ionic conductor. The electrolyte 3 may in particular be an anionic conductor, more specifically an anionic conductor of O ² ions, and the electrolyzer is then called anionic electrolyzer, as opposed to protonic electrolytes (H ⁺ ).

The electrochemical reactions are at the interface between each of the electronic conductors and the ionic conductor.

At cathode 2, the half-reaction is as follows:

2H ₂ O + 4e - ^ 2H ₂ + 2O ^{2 "} .

At anode 4, the half-reaction is as follows:

2 0 ² 0 ₂ + 4 e

The electrolyte 3, interposed between the two electrodes 2 and 4, is the place of migration of O ² ions under the effect of the electric field created by the potential difference. imposed between the anode 4 and the cathode 2.

As illustrated in parentheses in FIG. 1, the water vapor at the cathode inlet may be accompanied by hydrogen H ₂ and the hydrogen produced and recovered at the outlet may be accompanied by water vapor. Likewise, as illustrated in dashed lines, a draining gas, such as air, can also be injected at the inlet to evacuate the oxygen produced. The injection of a draining gas has the additional function of acting as a thermal regulator.

An electrolyzer, or elementary electrolysis reactor consists of an elementary cell as described above, with a cathode 2, an electrolyte 3, and an anode 4, and two mono-polar connectors which provide the functions of electrical, hydraulic and thermal distribution.

To increase the flow rates of hydrogen and oxygen produced, it is known to stack several elementary electrolysis cells on each other by separating them by interconnection devices, usually called interconnectors or bipolar interconnection plates. The assembly is positioned between two end interconnection plates that support the power supplies and gas supplies to the electrolyser (electrolysis reactor).

A high temperature solid oxide electrolyser (SOEC) thus comprises at least one, generally a plurality of electrolysis cells stacked one above the other, each elementary cell being formed of an electrolyte, a cathode and a anode, the electrolyte being interposed between the anode and the cathode.

As indicated above, the fluidic and electrical interconnection devices that are in electrical contact with one or more electrodes generally provide the power supply and collection functions and define one or more gas circulation compartments.

Thus, a so-called cathodic compartment has the function of distributing electric current and water vapor as well as recovering hydrogen from the cathode in contact.

An anode compartment has the function of distributing the electric current and recovering the oxygen produced at the anode in contact, possibly using a draining gas.

FIG. 2 represents an exploded view of elementary patterns of a high temperature solid oxide electrolyser (SOEC) according to the prior art. This electrolyser comprises a plurality of elementary electrolysis cells C1, C2, of solid oxide type (SOEC), stacked alternately with interconnectors 5. Each cell C1, C2 consists of a cathode 2.1, 2.2 and an anode (only the anode 4.2 of the cell C2 is shown), between which is disposed an electrolyte (only the electrolyte 3.2 of the cell C2 is shown).

The interconnector 5 is a metal alloy component which provides the separation between the cathode compartment 50 and the anodic compartment 51, defined by the volumes between the interconnector 5 and the adjacent cathode 2.1 and between the interconnector 5 and the adjacent anode 4.2. respectively. It also ensures the distribution of gases to the cells. The injection of water vapor into each elemental pattern is done in the cathode compartment 50. The collection of the hydrogen produced and the residual water vapor at the cathode 2.1, 2.2. is performed in the cathode compartment 50 downstream of the cell C1, C2 after dissociation of the water vapor therefrom. The collection of the oxygen produced at the anode 4.2 is carried out in the anode compartment 51 downstream of the cell C1, C2 after dissociation of the water vapor therefrom. The interconnector 5 ensures the passage of the current between the cells C1 and C2 by direct contact with the adjacent electrodes, that is to say between the anode 4.2 and the cathode 2.1.

FIG. 3 represents an exploded view of elementary patterns of a solid oxide fuel cell (SOFC) according to the prior art. The same elementary patterns as those of FIG. 2 are implemented for a SOFC fuel cell with cells of elementary cells C1, C2 and interconnectors 5. The cathodes 2.1, 2.2 of the electrolyser previously described with reference to FIG. 2 are then used as anodes for an SOFC cell and the anodes 4.1, 4.2 as cathodes. Thus, for SOFC battery mode operation, the injection of oxygen-containing air into each elemental pattern is done in the compartment which has become cathodic 51. The collection of the water produced at the anode is carried out in the compartment become anodic 50 downstream of the C1, C2 cell, after recombination in water of the H ₂ dihydrogen injected at the anode 2.2 into each anode compartment 50 upstream of the cell C1, C2 with the ions O ^{2 ~} having passed through the electrolyte 3.2. The current produced during the recombination of the water is collected by the interconnectors 5.

The operating conditions of a high temperature solid oxide electrolyser (SOEC) being very close to those of a solid oxide fuel cell (SOFC), the same technological constraints are found, namely mainly the mechanical resistance to the temperatures and thermal cycles of a stack of different materials (ceramics and metal alloy), maintaining the tightness of the anode and cathode compartments, the aging resistance of the metal interconnectors and the minimization of the ohmic losses at various interfaces of the stack.

An important constraint is to best manage the thermal operating conditions of a solid oxide fuel cell (SOFC) in which the hydrogen oxidation reaction is highly exothermic, or a water electrolyser at high temperature (EHT) where the overall reaction can be either exothermic or endothermic, or generally isothermal (autothermal operation) depending on the operating potential.

In particular for the highly exothermic reaction of a solid oxide fuel cell (SOFC), it is necessary to provide means for cooling the system. Thus, to allow cooling and to limit the temperature gradient in the stack, without impairing the fuel utilization rate (defined as the percentage of incoming reactants consumed by the reaction within the stack), the main variable of Possible adjustment is the air flow on the cathode side, compared to the need for the electrochemical reaction. If this technique remains relatively acceptable at low pressure, the overconsumption of gas compressors, resulting from the increase in the amount of gas to be compressed upstream of the SOFC stack, quickly becomes prohibitive for the overall energy efficiency at higher pressure. Alternative solutions have already been envisaged in the prior art for this type of technology, and in particular to allow such cooling of the system during the exothermic reaction of oxidation of hydrogen in a SOFC stack.

Thus, several patent documents already exist at the level of the electrolyser object in order to maintain the temperature within the acceptable limits of the system. It can thus be noted patent documents highlighting the heat exchange between the stack and the enclosure containing it, such as patent application US 2006/0105213 A1 which proposes to extend the interconnector plates to form exchange fins thermal, or the international application WO 2013/060869 A1 which has thick interconnected plates profiled so as to improve the heat transfer by radiation. Other patent documents put forward the possibility of using a heat-transfer fluid, distinct from the cathode and anode gases, directly within the stack in order to evacuate the heat produced, such as the GB 2 patent application. 151,840.

For thermal management of a stack at the system level, the US patent application US 2009/0263680 A1 describes the use, in an embedded system, of a non-reactive heat transfer fluid (air, steam, etc.). ) injected through the SOFC stack in order to bring thermal inertia to the cells, and thus easily evacuate the heat of reaction. The goal is to obtain efficient cooling of the cell, with the possibility of producing additional electricity through a downstream turbine taking advantage of the heating of the coolant. In addition, recycling of a portion of the heat transfer fluid to the inlet of the cell is provided to allow preheating of the incoming gas.

However, this US patent application 2009/0263680 A1 does not provide for upgrading the excess heat produced by the SOFC battery other than through the downstream turbine producing electricity. In addition, it does not indicate how the heat transfer fluid dissipates heat within the cell. The invention in this document is also specific to embedded systems, so low power, unlike stationary systems of medium power and / or strong. In addition, the embedded system described in patent application US 2009/0263680 A1 is not designed to operate at high pressures, but instead uses low pressure indoor air or pressurized air as air flows around the battery.

In addition, the patent application US 2004/0081859 A1 still describes an SOFC stack capable of storing heat used in a heat storage material in discharge mode, and then using it to heat the water to be electrolyzed in charge mode. .

In addition, several publications deal with tests of hydrogen fuel cell systems. By way of example, the article entitled "Coupling and thermal integration of a solid oxide fuel cell with a magnesium hydride tank", B. Delhomme, A. Lanzini, International journal of hydrogen energy, 2013, 38, 4740-4747, envisages the coupling of a hydrogen cell with a hydride reservoir, while providing for a total recirculation of the unconsumed hydrogen after condensation of the water created by the electrochemical reaction within the cell. It thus seems possible to have a system conversion rate of hydrogen close to 100%.

Nevertheless, this solution was only thought for a low pressure operation, and is not concerned with a recompression of recirculated hydrogen. The thermal integration is succinct. An assembly is provided to allow heat recovery for desorption, but it involves the combustion of the unreacted hydrogen at the stack outlet, rather than aiming for a conversion rate of 100%.

There is still a need to improve the management of the thermal operating regimes of a high temperature water electrolyser (EHT) and a solid oxide fuel cell (SOFC), in particular to overcome the exothermicity of the reactions. considered, especially during operation under pressure.

DISCLOSURE OF THE INVENTION The object of the invention is to remedy at least partially the needs mentioned above and the drawbacks relating to the embodiments of the prior art.

The invention thus has, according to one of its aspects, a system for the reversible electrolysis of water at high temperature, characterized in that it comprises: a high temperature reversible electrolyser device configured to operate in a SOEC type solid oxide electrolyser mode for the production of hydrogen and thus the storage of electricity, and / or in a fuel cell mode. solid oxide of the SOFC type, for the consumption of hydrogen and thus the destocking of electricity, said reversible electrolyser being configured to operate at a pressure of between 2 and 15 bar, in particular between 8 and 12 bar,

a hydride reservoir, thermally coupled with said reversible electrolyser, configured to store the hydrogen in hydride form in solid oxide electrolyser mode of the SOEC type of said reversible electrolyser and / or to release the hydrogen in the solid oxide fuel cell of the SOFC type of said reversible electrolyser,

the system being configured to allow, when the reversible electrolyser is configured to operate in a SOEC type solid oxide electrolyser mode, a recovery of the heat released by the hydride reservoir during the absorption of hydrogen for producing the pressurized water vapor to enter the reversible electrolyser, and to permit, when the reversible electrolyser is configured to operate in SOFC type solid oxide fuel cell mode, heat recovery released by the outflow (s) of the reversible electrolyser to allow the desorption of hydrogen from the hydride reservoir.

Advantageously, the operation of the system according to the invention makes it possible to limit the work of compressing gases, in particular hydrogen, since only liquid water is compressed. The system according to the invention may further comprise a compressor for compressing the liquid water. This thus makes it possible to improve the yields with respect to a system operating the reversible electrolyser at atmospheric pressure. The operation of the electrolyser under pressure also makes it possible to improve its performances, in particular by reducing the diffusion limit phenomena of the reactive species within the cells.

The reversible electrolysis system according to the invention may further comprise one or more of the following characteristics taken separately or in any possible technical combination. By the terms "reversible electrolysis" and "reversible electrolyser" is meant respectively that the electrochemical reaction of electrolysis of water at high temperature (EHT) can be carried out in one direction and / or in the other, namely that it can allow the production of hydrogen and / or hydrogen consumption depending on the operating mode of the system, and that the reversible electrolyser can operate in a storage mode and / or a destocking mode. More precisely, in the storage mode, it allows the production of hydrogen and thus the storage of electrical energy. Conversely, in the destocking mode, it allows the consumption of hydrogen and thus the destocking (or the restitution) of electrical energy.

In addition, throughout the description, the terms "upstream" and "downstream" are to be considered in relation to the direction of flow of the flow in question, namely from upstream to downstream.

Of course, the system according to the invention can be of modular design. In particular, it may comprise a plurality of reversible electrolysers and / or hydride reservoirs. Thus, all or part of these electrolysers and / or hydride tanks can be activated, depending in particular on the desired power range.

The reversible electrolyser may especially comprise a stack of elementary electrochemical cells with solid oxides each formed of a cathode, an anode and an electrolyte interposed between the cathode and the anode, and a plurality of electrical interconnectors and fluidics each arranged between two adjacent elementary cells.

Each interconnector may be conventional as described in the prior art or the so-called "three-stream" type. In particular, each interconnector can integrate a stack architecture allowing the heat exchange between the cathode and anode gases with a third fluid having the role of heat transfer fluid. This heat transfer fluid can circulate in the chamber, provided that the stack has an architecture allowing a suitable heat exchange, as proposed, inter alia, in the patent application US 2006/0105213 A1 or the international application WO 2013/060869 A1, previously described. This coolant can also circulating within the stack in separate channels, as proposed in the patent application GB 2 151 840 A, described above. It should also be noted that the enclosure makes it possible to work in pressure, this one complying in particular with the Directive DESP97 / 23 / CE to allow to work between 2 and 15 bars.

In addition, the reversible electrolyser may be configured to operate in a SOEC-type solid oxide electrolyser mode, and the system may then include a steam generator for producing water vapor for the reversible electrolyser by means of the heat released by the hydride reservoir, during the absorption of hydrogen, and supplied to the steam generator by means of a coolant.

The system may further include one or more heat exchangers for preheating the system inlet water and / or superheating of the water vapor entering the reversible electrolyser through the hydrogen streams. and outgoing oxygen from the reversible electrolyser. The system may in particular comprise heat exchangers upstream and downstream of the steam generator for respectively allowing the preheating of the inlet water of the system and the superheating of the steam entering the reversible electrolyser. , through the outgoing hydrogen and oxygen streams of the reversible electrolyser.

The system may further include a condenser, coupled to a phase separator, for receiving the unreacted water vapor in the reversible electrolyzer and the dihydrogen produced by the reversible electrolyzer and condensing the unreacted water to allow its recycling within the system. The hydrogen produced can then be collected in the phase separator and sent to the hydride reservoir.

The system may further comprise a compression pump, intended to compress the inlet water of the system to a pressure of between 2 and 15 bars, in particular 8 and 12 bars.

The system may also include an electric heater upstream of the reversible electrolyser, providing additional superheating of water vapor, in particular up to 800 ° C. The system may also include a dryer, upstream of the hydride reservoir and downstream of the condenser, for removing the moisture contained in the hydrogen before storage in the hydride reservoir.

The system may also comprise a cold unit connected to the condenser, upstream of the phase separator, intended to ensure the condensation of the unreacted water vapor coming from the reversible electrolyser.

Moreover, the reversible electrolyser can be further configured to operate in a solid oxide fuel cell mode of the SOFC type under pressure, and the system may then include at least one heat exchanger, for preheating at least one incoming flow. in the reversible electrolyser through at least one outgoing flow of the reversible electrolyser.

The reversible electrolyser may be configured to operate in a solid oxide fuel cell mode of the SOFC type, and the system may further include at least one heat exchanger for recovering high temperature heat from at least one flow leaving the reversible electrolyser by means of at least one coolant, in particular to allow the desorption of hydrogen from the hydride reservoir.

Advantageously, there is no depressurization between the SOFC type solid oxide fuel cell mode and the SOEC type solid oxide electrolyser mode.

The reversible electrolyser may be configured to operate in a solid oxide fuel cell mode of the SOFC type, and the system may be of the "recirculating compressed air system" type consisting of a hydrogen circuit and a primary circuit air.

The reversible electrolyser may be configured to operate in a solid oxide fuel cell mode of the SOFC type, and the system may further be of the "three flow system" type, consisting of a hydrogen circuit, a primary air circuit and a cooling circuit using a "three-stream" type interconnector.

The dihydrogen circuit may comprise: means for mixing hydrogen from the hydride reservoir with total recycling of the hydrogen that is not consumed in the reversible electrolyser over a pressure range of 2 to 15 bars,

a heat exchanger for preheating the flow of dihydrogen entering the reversible electrolyser through the flow of dihydrogen leaving the reversible electrolyzer,

a heat exchanger forming a heat recovery device for recovering high temperature heat from the flow of dihydrogen leaving the reversible electrolyser by means of at least one coolant.

The system may further comprise a heat exchanger, intended to cool the flow of hydrogen out of the heat exchanger, forming heat recovery, by the flow of hydrogen leaving a phase separator, allowing the recovery of heat. produced water.

In the case of a system of the "recirculating compressed air system" type, the primary air circuit may comprise:

- an air compressor to have air between 2 and 15 bar,

a heat exchanger for preheating the flow of air entering the reversible electrolyser through the flow of air leaving the reversible electrolyser,

- A heat exchanger forming a heat recovery device for recovering high temperature heat from the air flow leaving the reversible electrolyser through at least one heat transfer fluid.

The system may further comprise means for mixing the airflow leaving the heat exchanger, forming a heat recovery unit, with a complement of oxygen forming a total flow of air entering the reversible electrolyser. from 2 to 15 bars.

The system can still include:

a heat exchanger and a cooling device, for cooling the total flow of air mixed by the mixing means,

- A compression pump, for compressing the air leaving the cooling device before injection in the heat exchanger for its preheating. This pump makes it possible to compensate the pressure drops of the system and to raise the pressure to the right input level (2 to 15 bars).

In the case of a "three flow" type system, the primary air circuit may comprise:

- an air compressor to have air between 2 and 15 bar,

a heat exchanger for preheating the flow of compressed air entering the reversible electrolyser by means of the air flow leaving the reversible electrolyser,

In the case of a system of the "three flow" type, the cooling circuit may further comprise:

a heat exchanger for preheating the flow of heat transfer medium under pressure entering the reversible electrolyser via the hot flow leaving the reversible electrolyser,

a heat exchanger forming a heat recovery device for recovering high temperature heat from the hot flow leaving the reversible electrolyser via at least one coolant,

a heat exchanger and a cooling device, also designated by supercooling device, for cooling the hot flow leaving the heat exchanger,

a compression pump, intended to compress the flow exiting the heat exchanger and the supercooling device, to form a compressed fluid flow over the range of 2 to 15 bar to cool the hot flow exiting the heat exchanger. This pump makes it possible to compensate only the pressure losses of the system and to raise the pressure to the right input level (2 to 15 bars).

In another aspect, the subject of the invention is also a method for storing and / or releasing electricity by reversible electrolysis of water at high temperature, characterized in that it is implemented by means of a system reversible electrolysis of water at high temperature as defined above, and in that it comprises the steps of:

when the reversible electrolyser under pressure operates in a solid oxide electrolyser type SOEC mode, recovery of the heat released by the hydride reservoir during the absorption of hydrogen to produce the water vapor under pressure intended to enter the reversible electrolyser, and

when the reversible electrolyser under pressure is configured to operate in a solid oxide fuel cell mode of the SOFC type, recovery of the heat released by the outflow (s) of the reversible electrolyzer to allow the desorption of hydrogen hydride tank.

The method may be implemented according to an electricity storage mode, the high temperature reversible electrolyser being configured to operate in a SOEC solid oxide electrolyser mode, and the method may include the step of performing the high-temperature electrolysis reaction of the pressurized water vapor to produce hydrogen and thus store electricity.

The method can particularly be implemented according to the storage mode by means of a reversible electrolysis system of water at high temperature, and can comprise the following successive steps:

- introduction of the total water of the system, comprising injection water and recycled water from the phase separator, in the compression pump to a pressure of between 2 and 15 bar, in particular between 8 and 12 bars,

- circulation of the total water of the system through heat exchangers to allow preheating of the inlet water of the system through the outgoing hydrogen and oxygen flows of the reversible electrolyser,

- introduction of the system inlet water into the steam generator, to produce the pressurized water vapor to the reversible electrolyzer by means of the heat released by the hydride reservoir, during the absorption of hydrogen, and supplied to the steam generator by a coolant, - circulation of water vapor through heat exchangers to allow superheating of water vapor before entering the reversible electrolyser, through the outgoing hydrogen and oxygen streams of the reversible electrolyzer,

- additional superheating of the steam to reach the working temperature of the electrolyser using an electric heater,

- introduction of water vapor under pressure in the reversible electrolyzer for the production of hydrogen and oxygen streams,

- cooling of hydrogen and oxygen flows through heat exchangers,

condensation of unreacted water vapor in the phase separator to produce recycled water reintroduced into the system,

storage of the dried product hydrogen in the hydride reservoir.

Advantageously, there is no compression of hydrogen between the electrolyser and the reservoir.

The method can also be implemented according to an electricity destocking mode, the high temperature reversible electrolyser being configured to operate in a solid oxide fuel cell mode of SOFC type under pressure, and the method can comprise the step of performing the reverse reaction of electrolysis at high temperature of the water vapor to consume hydrogen and thus destocking electricity.

The method can also be particularly implemented in the destocking mode by means of a reversible water electrolysis system at high temperature of the "recirculating compressed air system" type, and may comprise the following successive steps:

• for the dihydrogen circuit:

mixing hydrogen from the hydride reservoir at the targeted pressure of 2 to 15 bars, with the total recycling of the hydrogen that is not consumed in the reversible electrolyzer by means of mixing means, injection of the total hydrogen through the heat exchanger allowing its preheating by the flow of hydrogen leaving the reversible electrolyser,

injection of total hydrogen into the reversible electrolyser for its consumption and the production of water, electricity and heat,

cooling the flow of hydrogen leaving the reversible electrolyser by the preheating heat exchanger,

cooling the hydrogen flow exiting the preheating heat exchanger through the heat exchanger, forming a heat recovery device, making it possible to recover the heat by exchanging it with a heat transfer fluid,

separation between the flow of hydrogen and the flow of water produced from the condenser,

- recycling of unused hydrogen by recompressing only the value of the losses,

• for the primary air circuit:

- injection of the air leaving the reversible electrolyser through the cooling heat exchanger to be cooled by the compressed air entering the reversible electrolyser,

- Injection of the air exiting the cooling heat exchanger through the heat exchanger, forming a heat recovery unit, through which a heat transfer fluid passes,

mixing air leaving the heat exchanger, forming a heat recovery device, by means of mixing with a complementary flow of compressed oxygen,

injecting this mixture into a heat exchanger, then a cooling device, then a compression pump to compensate the pressure losses and to obtain compressed air injected into this cooling heat exchanger downstream of the mixing means ,

injection of the air coming from the cooling heat exchanger into the heat exchanger for its preheating, then injection into the reversible electrolyser at the targeted pressure of 2 to 15 bar. The method can also be particularly implemented in the destocking mode by means of a reversible electrolysis system under high temperature water pressure of the "three-flow system" type, and may comprise the following successive steps:

· For the dihydrogen circuit:

mixing hydrogen from the hydride reservoir with the total recycling of the hydrogen that is not consumed in the reversible electrolyzer by means of mixing means,

injection of the total hydrogen at the targeted pressure of 2 to 15 bars through the heat exchanger allowing it to be preheated by the flow of hydrogen leaving the reversible electrolyser,

injection of total hydrogen at the targeted pressure of 2 to 15 bars in the reversible electrolyser for its consumption and the production of water, electricity and heat,

separation between the flow of hydrogen and the flow of water produced from the phase separator,

- recycling of the unused hydrogen by recompressing only the value of the pressure losses of the assembly,

• for the primary air circuit:

injecting ambient air into a compression pump until a pressure of between 2 and 15 bar, in particular between 8 and 12 bar,

preheating of the air entering the preheating heat exchanger via the air flow leaving the reversible electrolyser,

injection of the incoming air preheated in the reversible electrolyser at the target pressure, cooling of the air leaving the reversible electrolyser in the preheating heat exchanger,

cooling the air leaving the preheating heat exchanger through the heat exchanger, forming a heat recovery device, to obtain heat by means of at least one coolant,

- Injection of the air leaving the heat exchanger, forming a heat recovery unit, in a gas turbine to eject the outgoing air,

• cooling system :

cooling of the hot flow leaving the reversible electrolyser through the preheating heat exchanger by the fluid entering the reversible electrolyser,

cooling the flow exiting the preheating heat exchanger in the heat exchanger, forming a heat recovery unit, by means of at least one coolant,

total cooling of the flow exiting the heat exchanger, forming a heat recuperator, in a heat exchanger by the recompressed fluid flow,

- Injection of the flow exiting the heat exchanger traversed by the recompressed fluid flow in a cooling device, also designated by supercooling device, then a compression pump,

preheating the flow leaving the compression pump by the flow leaving the reversible electrolyser before entering the reversible electrolyser at the target pressure of 2 to 15 bar, in particular 8 to 12 bar.

The reversible electrolysis system under pressure and the electrolysis process according to the invention may comprise any of the features set forth in the description, taken alone or in any technically possible combination with other characteristics. BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be better understood on reading the following detailed description, non-limiting examples of implementation thereof, as well as on examining the schematic and partial figures of the appended drawing. on which :

FIG. 1 is a schematic view showing the operating principle of a high temperature solid oxide electrolyser (SOEC),

FIG. 2 is an exploded schematic view of part of a high temperature solid oxide electrolyser (SOEC) comprising interconnectors according to the prior art,

FIG. 3 is an exploded schematic view of part of a solid oxide fuel cell (SOFC) comprising interconnectors according to the prior art,

FIG. 4 is a block diagram showing an example of a high temperature reversible water electrolysis system according to the invention, comprising a high temperature reversible electrolyser, operating in a solid oxide electrolyser mode of the type SOEC,

FIG. 5 represents, in graphic form, the evolution of the PCI performance of a system according to the invention operating in hydrogen production mode and with a nominal value of 116 kW AC, as a function of the electrical power. total consumption,

FIG. 6 is a block diagram showing the dihydrogen circuit of an example of a "recirculating air recirculation" system for the reversible electrolysis of water at high temperature in accordance with the invention, comprising a reversible electrolyser high temperature, operating in a solid oxide fuel cell mode of the SOFC type,

FIG. 7 is a block diagram showing the primary air circuit of the system of FIG. 6,

FIG. 8 represents, in graphic form, the evolution of the air flow rate of a system according to the invention as a function of the net electric power of the process corresponding to FIGS. 6 and 7, and a nominal power of 64 kW, FIG. 9 represents, in graphical form, the evolution of the PCI efficiency of the process of FIG. 8 as a function of the net electrical power of the process,

FIG. 10 represents, in graphic form, the evolution of the dihydrogen consumption of the process of FIG. 8 as a function of the net electrical power of the process,

FIG. 11 is a block diagram showing the dihydrogen circuit of an example of a so-called "three flow" system for the reversible electrolysis of water at high temperature in accordance with the invention, comprising a high temperature reversible electrolyzer, operating in a solid oxide fuel cell mode of the SOFC type,

FIG. 12 is a block diagram showing the primary air circuit of the system of FIG. 11,

FIG. 13 is a block diagram showing the cooling circuit of the system of FIG. 11,

FIG. 14 represents, in graphic form, the evolution of the primary air and cooling air flow rates of a system according to the invention as a function of the net electrical power of the corresponding process,

FIG. 15 represents, in graphical form, the evolution of the PCI performance of the process of FIG. 14 as a function of the net electric power of the process (AC), and

FIG. 16 represents, in graphic form, the evolution of the dihydrogen consumption as a function of the net power of the process of FIG. 14.

In all of these figures, identical references may designate identical or similar elements.

In addition, the different parts shown in the figures are not necessarily in a uniform scale, to make the figures more readable. DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS

FIGS. 1 to 3 have already been described previously in the section relating to the state of the prior art and to the technical context of the invention.

It is specified that, for all of the figures, the symbols and the arrows for supplying water vapor H ₂ O, for distribution and for recovery of H ₂ dihydrogen, of oxygen 0 ₂ , of air and of electric current, are shown for the sake of clarity and accuracy, to illustrate the operation of the devices shown.

In addition, it should be noted that all the constituents (anode / electrolyte / cathode) of a given electrolysis cell are ceramics. The operating temperature of a high temperature electrolyser is also typically between 600 and 1000 ° C.

Referring to Figure 4, there is shown in the form of a block diagram an example of a system 10 for reversible electrolysis of water at high temperature according to the invention, comprising a reversible high temperature electrolyser 11, operating in a SOEC solid oxide electrolyser mode for the production of hydrogen and thus the storage of electricity. In addition, the system 10 operates at a pressure of between 2 and 15 bar, or even between 8 and 12 bar.

The reversible electrolyser 11 is thermally coupled to a hydride reservoir 12, for storing hydrogen in the form of hydrides. The operating principle of the system 10 according to the invention shown in FIG. 4 will be described later in the section relating to the storage mode.

The reversible electrolysis system 10 of water at high temperature according to the invention may have several possibilities of use.

In particular, and without limitation, the system 10 can operate in a reversible mode, that is to say, both for storage and retrieval of electricity. In this case, a massive storage of electricity can be performed before its return by reversibility of the electrolysis process. The system 10 can still operate in a non-reversible mode, that is to say in an operation such that it is dedicated to only one of the two possible directions of the electrochemical electrolysis reaction.

More precisely, the system 10 can thus operate in a storage mode only: then, the system is similar to a station dedicated to the production of hydrogen filling the hydride reservoir 12 as well as to the supply of oxygen or hydrogen. enriched air. In this case, the system can for example serve as a charging station for a hydrogen vehicle, such as a construction machine.

The system 10 can still operate in a destocking mode only: then, the system is similar to a station dedicated to the production of electricity, which can be fed with hydrogen from the hydride reservoir 12 and / or another process . In the case of using hydrogen from another process, the latter can be injected via the hydride reservoir, in which case it acts as a buffer tank, or directly downstream of the reservoir. hydrides. In the case where one does not use hydrogen from a hydride-type storage, the heat recovered on the exchangers 31, 39 (case of the air recirculation system, FIGS. 6 and 7) or 31 , 42 and 91 (in the case of the 3-flow system, Figures 11, 12 and 13) must be evacuated, and may be used in other processes external to the system.

When the system 10 is used in a non-reversible mode of operation, either for the storage of electricity or for the destocking of electricity, certain elements of the system 10 may not be used, in particular certain networks of exchangers.

Next will be described below, with reference to Figures 4 to 16 the two main operating modes of the system 10 according to the invention, namely the storage mode and destocking mode. More specifically, Figures 4 and 5 relate to the operation of the system 10 according to the storage mode, and Figures 6 to 16 relate to the operation of the system 10 according to the destocking mode.

Stockfile mode

The electricity storage mode of the system 10 according to the invention uses the reversible electrolyser 11 in an operating configuration of an electrolyser solid oxide SOEC type. As represented in FIG. 4 and in accordance with the preceding description of this type of electrolyser, the SOEC electrolyser 11 comprises a stack of elementary electrochemical cells with solid oxides each formed of a cathode, which are generally called the cathode C of the cathode. SOEC electrolyser 11, which are generally called the anode A of the SOEC electrolyser 11, an electrolyte interposed between the cathode and the anode of each cell, and a plurality of electrical and fluidic interconnectors each arranged between two adjacent elementary cells, which are generally called the three-stream interconnector F3 of the SOEC electrolyser 11. However, preferentially, this three-stream interconnector F3 is not used in storage mode of the system 10 according to FIG. invention. Also, the parts relating to the operation of the three-stream interconnector F3 are shown in dashed lines in FIG. 4.

Solid oxide electrolysers of the SOEC type are capable of operating with or without air sweeping on the oxygen production side. They are able to supply almost pure oxygen as well as enriched air, as needed. In the system example 10 described here, it is considered that there is no air sweep in storage mode, which avoids the compression of this gas for the pressure operation envisaged, and that therefore the production of compressed and almost pure oxygen is obtained.

The storage mode of the system 10 according to the invention aims to produce hydrogen under pressure, which is then stored in the hydride tank 12, from electricity.

Advantageously, the SOEC electrolyser 11 is configured to operate at a pressure ranging from 2 to 15 bars, or even from 8 to 12 bars. Indeed, working in pressure in the SOEC electrolyser 11 limits the compression work of the hydrogen created, because compressing liquid water requires much less energy than compressing hydrogen.

However, it is conceivable to work on the electrolyser at a pressure different from that of the storage. This variant, however, would require a compressor (where the storage is at a pressure greater than the electrolyser) or a valve of relaxation (where storage is at a lower pressure) between the electrolyser and storage. The heat of absorption of hydrogen in the hydride would in any case be used to meet the needs of the steam generator.

Operation in storage mode is described below. Thus, as shown in Figure 4, deionized water H ₂ 0, represented by the arrow FH ₂ O is mixed with the M in water recovery H ₂ O _r ECUP the method, after the phase separator 13 Then, all H ₂ O _t otai of this water H ₂ 0 + H ₂ O _r ecup is compressed by a compression pump 14 to the working pressure, between 2 and 15 bar, or even 8 and 12 bar .

The total water H ₂ O _t otai is then separated into two streams fl and f2 by a separator

15, each stream f1, f2 being respectively preheated to saturation by heat exchangers 16 and 17 respectively crossed by flows of oxygen 0 ₂ and hydrogen H ₂ tiédis.

The water preheated through the two heat exchangers 16 and 17 is then remixed in M2, then brought to a boil in a steam generator 18 via the heat recovered in the hydride reservoir 12, at the same time. hydrogen absorption (e.g., about 75 kJ / mole for magnesium hydride hydride) via a heat transfer fluid FC. It is also appropriate to choose a metal hydride and a pressure range of the system 10 such that the heat released by the hydride is at a temperature greater than that of the boiling point of the water at the pressure considered as input electrolyzer, for example magnesium hydride is at the equilibrium of sorption at 380 ° C to 10 bar.

The water vapor is then separated again into two streams f3 and f4 by a separator 19, each stream f3, f4 being respectively superheated to between 670 and 750 ° C by heat exchangers 20 and 21 respectively crossed by flow of oxygen O ₂ and hydrogen H ₂ hot, leaving the SOEC electrolyser 11.

The two flows f3 and f4 superheated water vapor are then remixed in M3, then an electric heater 22 ensures the end of the superheat of the steam up to 700 to 800 ° C operating SOEC electrolyser 11 before to enter. Oxygen 0 ₂ and hydrogen H ₂ , respectively derived from anode A and cathode C, are cooled first respectively by heat exchangers 20 and 21 with the inlet water vapor of the streams f3 and f4, then respectively by the heat exchangers 16 and 17 with the water flows fl and f2.

With regard to oxygen 0 ₂ , it is stored or evacuated, represented by the arrow Fo ₂ .

With regard to the hydrogen H ₂ , a condenser 23 condenses the unreacted vapor, and this water is then collected in the phase separator 13 before being sent to the beginning of the M1 process for recycling. The hydrogen H ₂ finishes being dried in a dryer 24 before being sent into the hydride reservoir 12 for storage, which then produces heat recovered by the heat transfer fluid loop FC for the generator. 18. The dryer 24 may be of different types, such as a silica gel or a cryogenic trap. However, it must be able to remove the moisture present in the hydrogen H ₂ before entering the hydride storage tank 12. In fact, these compounds react strongly with water, it could damage the tank 12 and create a strong release of heat.

It should be noted that the system 10 can also operate with a SOEC 11 electrolyser in the exothermic mode, that is, the gases exiting the cells are hotter than those entering them, in which case the electric heater 22 is not necessary when operation of the SOEC 11 electrolyser.

It should be noted that the system 10 may also operate with a SOEC 11 electrolyser in endothermic mode, i.e. the gases exiting the cells are cooler than those entering it, in which case the electric heater 22 operates at a higher power for compensate for.

Advantageously, the thermal coupling between the SOEC electrolyser 11 and the hydride reservoir 12 provides several advantages. In particular, it makes it possible to supply the energy need of the steam generator 18, and thus makes it possible not to have to resort to a source external to the system 10, of the electric type or by combustion of gas, which then makes it possible to increase the efficiency of the electrolysis process in storage mode. In addition, such a thermal coupling also makes it possible to avoid having to evacuate the heat from the hydride reservoir 12, as is the case with the coupling between the hydride reservoir and low temperature electrolysis. This would otherwise have a significant cost in energy, which can reduce the efficiency of the process if no means of storing this heat is used, in which case a heat removal, such as a cooling tower, would be necessary. Advantageously, the electrolysis is carried out under pressure to avoid any compression of hydrogen before storage in the tank.

Example of realization

The high temperature reversible electrolyser 11 comprises an enclosure containing the stacks.

An exemplary embodiment of a SOEC electrolyser 11 thermally coupled to a hydride reservoir 12 in storage mode will now be described.

The different values given in the following example are derived from simulations carried out on the ProsimPlus software from thermodynamic models of electrolysis cells as well as auxiliaries (pumps, converters, etc.). The purpose of the system 10 of this example is to provide hydrogen absorbed on MgH magnesium hydride. The storage of the hydrides in the hydride reservoir 12 is at a pressure of 10 bars. The range of power of the system in production mode is between 115 and 116.5 kW, and the range of system efficiencies obtained is between 86.4 and 87.5% PCI (ratio between the lower heating value of the hydrogen gas created and the power consumption of the system). The output of the electrolyser stack alone is 97.5% PCI.

The system 10 thus comprises a storage of hydrogen hydrides hydride magnesium Mghh type. It absorbs cold hydrogen at about 35 ° C under a pressure of 10 bar, which releases energy of 75 kW / mole H ₂ as heat.

The heat generated by the absorption of hydrogen is recovered on a loop of heat transfer fluid FC, comprising oil, in order to feed the steam generator 18. The utilization rate in the electrolyser 11 is maintained sufficiently high, greater than about 60%, for storage at the hydride reservoir 12 to generate enough of heat to feed the steam generator 18 completely, namely total boiling water with overheating of 10 ° C.

The electrolyser 11 is controlled at the thermoneutral voltage in this example, with flow rates within the acceptable limits of the cells, ie from 12 to 48 NmL / min / cm ² . There is therefore no sweeping on the side of the anode, the oxygen produced being substantially pure. There is no cooling problem in the cells, the thermoneutral regime making it possible to obtain an electrolyser output temperature equal to that of the input. The third channel of the three-stream interconnector, represented by F3 in FIG. 4, is not used here. Restricting to the thermoneutral voltage has the effect of limiting the power range available to the storage mode system from endothermic or exothermic mode operation that provides a wider accessible range.

In the system efficiency calculations 10, it was compared the total heat of combustion that could potentially be released by the hydrogen produced with (PCS) or without (PCI) condensation of water generated with electrical energy (AC) required for its production at the full system level. The lower (PCI) and higher (PCS) calorific values of hydrogen are respectively 244 and 286 kJ / mol.

FIG. 5 represents, in graphical form, the evolution of the efficiency R of the system 10 operating in the hydrogen production mode for a system with a nominal value of 116 kW AC, as a function of the total electrical power consumed De, expressed in kW AC.

The yield R for the PCI curve is more precisely calculated with the following formula:

R = [H _{2 rate} created * PCI] / Power consumption.

The electrical consumptions taken into account in the yields include the consumption of the electrolyses cells themselves, to which are added the consumption of auxiliaries (pumps, hot and cold groups and power electronics).

Thus, the assembly of the system 10 in storage mode makes it possible to value the heat of absorption of the hydrogen on the hydride in an efficient manner, by providing a heat source for supplying the steam generator 18, which allows a saving on the power consumption of at least 15% compared to processes using low temperature electrolysis (PEM, alkaline), which they must remove this heat. This, coupled with the higher electrical efficiency of high temperature electrolysis compared to low temperature processes, explains the high values shown in the yields.

The yield is also higher than a conventional system because hydrogen is produced which is absorbed in the hydride, which releases heat used to power the steam generator. In the case of a system without heat supplied by the hydride, it would be necessary to provide the system by means of a hot utility the heat required by the steam generator, which would reduce the PCI and PCS efficiencies of respectively 15 and 17 points about.

Destocking mode

The destocking mode of electricity of the system 10 according to the invention uses the reversible electrolyser 11 in an operating configuration of a solid oxide fuel cell of the SOFC type.

In this destocking mode, the goal is to consume hydrogen in the fuel cell 11 at a pressure of between about 2 and 15 bar, with the objectives of providing electricity with a high efficiency, and possibly to provide heat at low temperatures to supply a heating network, such as a dwelling, an agricultural dryer, among others.

In the destocking mode, the system 10 can take the form of two separate systems, respectively called air recirculation system and three flow system. They are detailed below.

Recirculating air system

This system 10 is illustrated with reference to FIGS. 6 and 7. In this case, the system 10 is devoid of a three-flux type interconnector. As can be seen in FIGS. 6 and 7, the fuel cell 11 comprises an anode A and a cathode C, as previously described, but no third coolant channel. In this system 10, the cooling of the fuel cell 11 is only ensured by the flow of compressed air on the cathode side, which is therefore expected to be important because of the exothermicity of the oxidation reaction of the reactor. hydrogen. The desorption of hydrogen in the hydride reservoir is ensured by the collection of heat on the output fluids.

The operation of the hydrogen dihydrogen circuit H _{2 is} followed successively below, followed by the operation of the primary air circuit.

H2 dihydroqene circuit

This circuit is illustrated with reference to FIG. 6. In this FIG. 6, the parts in dashed lines refer to the primary air circuit detailed below with reference to FIG. 7. Advantageously, the hydrogen dihydrogen circuit H ₂ forms a loop for recycling the unconsumed hydrogen in the fuel cell 11. Thus a conversion close to 100% of the hydrogen is obtained.

The operation of the hydrogen circuit H ₂ in the destocking mode of a recirculating air system 10 is described below. Hydrogen H _2, from the hydride tank 12 under a pressure of 2 to 15 bars, or even 8 to 12 bar, is mixed with the Ml total recycle hydrogen H _2r ésiduei unconsumed in the stack fuel 11.

The total flow of hydrogen H ₂ totai then passes through a heat exchanger 30 to be preheated by the H ₂ output gas from the fuel cell 11. Then, it is injected into the fuel cell 11 to be oxidized and produce water, electricity and heat.

At the outlet of the fuel cell 11, the stream of hydrogen H ₂ is cooled through the heat exchanger 30 by the inlet gases H _2to tai, and then passes through a heat exchanger 31, forming a recovery device. heat at over 400 ° C, to recover heat by exchanging it with an FC heat transfer fluid, such as oil, air, steam, among others.

The stream of H2 hydrogen and water vapor passes through a heat exchanger 33 to be cooled by the flow of hydrogen H ₂ leaving a phase separator 34. After passing through the heat exchanger 33, the flow H ₂ passes through a condenser 35, then the phase separator 34 to allow the recovery of water H ₂ 0 produced, represented by the arrow FH ₂ O, and allow its evacuation for possible recovery.

At the outlet of the separator 34, the hydrogen H ₂ , which may contain a few traces of water, is heated by the incoming stream of hydrogen H ₂ passing through the heat exchanger 33, and is then sent to a compression pump 36 for to compensate the pressure losses of the circuit, before being mixed in M l with hydrogen from the hydride reservoir 12.

The hydride reservoir 12 may have any type of reservoir capable of returning hydrogen in the desired temperature ranges, of the order of 300 to 400 ° C., and in the desired pressure ranges, of the order of 2 to a dozen bars. However, the hydrides must have a hydride absorption temperature sufficient to serve the steam generator 18 in storage mode and that the battery releases sufficient heat to allow the desorption of the required amount of hydrogen to be reached. Operating.

The hydrogen circuit H ₂ may also comprise a purge valve, in order to be able to eliminate any neutral gases, such as nitrogen or argon, possibly present in the hydrogen storage.

Primary air circuit

This circuit is illustrated with reference to FIG. 7. In this FIG. 7, the dashed lines refer to the hydrogen circuit H ₂ detailed previously with reference to FIG. 6. The primary purpose of the compressed air circuit is to supplying the fuel cell 11 with oxygen 0 ₂ , as well as evacuating the heat produced by the battery 11.

The operation of the primary compressed air system in the destocking mode of an air recirculation system 10 is described below. The air leaving the fuel cell 11 passes through a heat exchanger 38 to be cooled by the air entering the fuel cell 11. Then, the air flow passes through a heat exchanger 39, forming heat recovery at more than 400 ° C, itself traversed by an FC heat transfer fluid comprising oil.

The air is then mixed in Ml with an oxygen flow O ₂ , represented by the arrow F02, then cooled through a heat exchanger 40 with recompressed air, and in a second cooling device 41 until at the recompression temperature, then compressed in a compression pump 42. The recompression is only the value of the pressure losses and not a complete recompression of 2 to 15 bars that one would have if one did not recirculate the air, which presents a substantial gain on the basis of the invention.

The compressed air is then put at the inlet temperature in the fuel cell 11 by passing through the heat exchangers 40 and 38, before being injected into the cathode C.

Depending on the hydrides used, and the desired operating ranges, the heat recovered for desorption may be insufficient. The addition of a burner operating with hydrogen and allowing the heat transfer fluid FC to recover the missing heat can then be considered. An auxiliary electric heater is also usable, but less efficient, because the cost of electricity can be high during operation in destocking mode, and this will impact the efficiency of the system.

Moreover, in case of need for additional heat to be recovered on the high temperature exchangers 38 and 39 described above, part of the hydrogen can be burned in a combustion chamber located upstream of the exchanger considered. This combustion chamber may for example be located upstream of the heat exchanger 39 of the primary air circuit, which makes it possible not to add an exchanger on the heat transfer fluid circuit FC, but makes necessary the condensation of the water thus created before recompression. The latter being performed cold, this can cause limited design problems. The combustion chamber can still be located on a burner independent of the hydrogen and air circuits, this assembly being simple to apply but less energy efficient because the air will have to to be preheated or the part of the combustion energy collected by the heat transfer fluid FC may be limited.

Advantageously, the recirculating air system allows the production of electricity, potentially carbon-free and / or renewable depending on the origin of the electricity to produce hydrogen in storage mode. In addition, it allows the production of heat at high temperature, required for the desorption of hydrogen in the hydride reservoir 12, with the possibility of burning a little hydrogen if the fuel cell 11 does not provide enough of herself. This eliminates the need for a high temperature heat source outside the system 10. In addition, it allows a range of electric power and / or achievable thermal that is wide around the nominal, here 75 to 100%. Finally, a slight improvement in efficiency is obtained with respect to a three-stream system, described below, because of the lower air compression due to its recirculation associated with 0 ₂ enrichment. In the three flow system only part of the air is recycled.

Example of realization

An embodiment of a SOFC fuel cell 11 thermally coupled to a hydride reservoir 12 in the destocking mode with a recirculating air system 10 will now be described. The different values given in the following example are derived from simulations carried out on ProsimPlus software from thermodynamic models of cell cells as well as auxiliaries (pumps, converters, etc.).

The purpose of the system 10 of this example is to provide electricity with high efficiency and wide power range. The storage of the hydrides in the hydride reservoir 12 is at a pressure of 10 bars. The power output range (AC, grid injectable) is between 49.5 and 65.3 kW, being between 51.2 and 68.2 kW for the fuel cell 11 (variant PCI output from 72% for operation at minimum power to 66% for its operation at maximum power), and the range of electrical efficiencies obtained for the system is between 59.5 and 60.5% PCI (lower calorific value of hydrogen out of the tank). An H ₂ burner is used in addition for the heat desorption for the regimes for which the heat collected on the oil loop is not sufficient.

The system 10 thus comprises a magnesium hydride MgH ₂ hydride hydrogen storage at a pressure of 10 bars and at 380 ° C., consuming 75 kJ per mole of H ₂ released. The high temperature heat recovered on the exchangers is used to desorb the hydrogen, as well as to mitigate the heat losses on the process. The hydride reservoir 12 requires the provision of a desorption energy equal to 75 kJ / (mole of desorbed H ₂ ) and a temperature greater than 380 ° C. By taking into account the pinching of the heat exchangers, only process heat above 400 ° C can be recovered for this purpose. It is also taken into account heat losses on the process, the stack 11 and the tank 12, 2.7 kW to compensate.

In the event of a lack of heat recovered on the heat exchangers, some of the desorbed hydrogen is burned to provide additional energy.

The flow rates of the different fluids were set in the following manner: for hydrogen H ₂ , the flow rate is constant and set at 12 NmL / min / (cm ² of cell); and for primary air, the flow rate is sufficient to limit the temperature in the cell 11 to 150 ° C.

Moreover, the cooling strategy is as follows: the temperature of the hydrogen entering the cell 11 is constant and equal to 700 ° C .; the temperature of the air entering the stack 11 is constant and equal to 600 ° C; the stack outlet temperature is kept constant and equal to 850 ° C for both flows; the primary air flow rate is set to maintain the constant battery outlet temperature, up to a maximum flow rate of 48 NmL / min / (cm ² of cell).

The results obtained are represented graphically in FIG. 8, which shows the evolution of the air flow Da, expressed in NmL / min / (cm ² of cell), as a function of the electric power P of the process, expressed in kW, and also in FIG. 9, which shows the evolution of the electrical efficiency R of the destocking method, expressed in percentages, as a function of the net power P of the process, expressed in kW, and finally in FIG. evolution of CH ₂ consumption into dihydrogen, expressed in g / h, as a function of the net power P of the process, expressed in kW. In this FIG. 10, the curve Ca represents the total consumption in H ₂ , and the curve Cb represents the consumption of burned H ₂ for additional heat.

The net power P of the process is defined as the AC power output of the battery 11 and the associated turbine (primary air circuit) to which the consumption of compressors and recirculators is deducted.

The yield R of the process is defined as follows:

R = Net power of the process P in AC injected on the network / [PCI H ₂ * Flow rate of H ₂ consumed]

The net power of the process corresponds to the power produced by the battery, which is subtracted the consumption of auxiliaries (compressors, cold groups and power electronics).

The system 10 thus makes it possible to operate over a wide range of power, while keeping a high electrical efficiency.

The process is thus able to take advantage of the storage of the hydride reservoir 12, which has as a strong point a high density of hydrogen storage (on MgH ₂ type hydride, the mass of 5% by weight of hydrogen is reached. ), without external heat input to desorb hydrogen, which a conventional system, such as a low temperature battery system (PEM, etc.) can not do.

Three flow system

This system 10 is illustrated by means of FIGS. 11, 12 and 13. In this case, the SOEC fuel cell 11 of the system 10 according to the invention comprises an interconnector 5 of the three-flow type (allowing the heat exchange with a cooling fluid distinct from the cathode and anode flows) as previously described, the presence of which in the fuel cell 11 is symbolized by the reference F3 in FIGS. 11, 12 and 13. In addition, as can be seen in FIG. see in these figures, the fuel cell 11 has anode A and a cathode C, as previously described. The heat transfer fluids referenced hereinafter on the different circuits of FIGS. 11, 12 and 13 are pooled in order to ensure the supply of heat necessary for the desorption of hydrogen from the hydride reservoir 12. The operation of the hydrogen circuit H _{2 is} followed successively below, then the operation of the primary air circuit and finally the operation of the cooling circuit that can be achieved by means of the three-flow interconnector.

H2 dihydrogen circuit

This circuit is illustrated with reference to FIG. 11. In this FIG. 11, the dashed portions refer to the primary air circuit and the cooling circuit detailed below with reference to FIGS. 12 and 13. Advantageously, the hydrogen circuit H ₂ forms a loop allowing the recycling of the unconsumed hydrogen in the fuel cell 11. A conversion close to 100% of the hydrogen is thus obtained.

The operation of the hydrogen circuit H ₂ in the destocking mode of a three-flow system 10 is advantageously substantially similar to that previously described for a recirculating air system.

Thus, reference should be made to the foregoing description stated for the exemplary embodiment of FIG. 6.

Primary air circuit

This circuit is illustrated with reference to FIG. 12. In this FIG. 12, the parts in dashed lines refer to the dihydrogen circuit H ₂ and to the cooling circuit detailed previously respectively and hereinafter with reference to FIGS.

11 and 13. The primary air circuit is intended to supply the fuel cell 11 oxygen 0 ₂ .

The operation of the primary air circuit in destocking mode of a system

10 to three streams is described below. Ambient air, represented by the arrow Fairi, is compressed in a compression pump 48 to the operating pressure, between 2 and 15 bar, or between 8 and 12 bar. Then, this air is preheated through a heat exchanger 47 by the output gases of the fuel cell 11 before being injected into the fuel cell 11 at the cathode C. The depleted and heated air leaves the fuel cell 11 and is then cooled by the heat exchanger 47 in which the air entering the fuel cell 11 flows.

Then the air passes through a heat exchanger 49, forming heat recovery, to recover the heat through the heat transfer fluid FC.

The air then passes through a turbine 43 to recover a maximum of the initial compression work, before being returned to the atmosphere, represented by the arrow F _a ir2, after a possible cooling to remove the remaining heat.

The compression pump 48 and the turbine 43 may have a common axis to maximize mechanical energy recovery.

Furthermore, it is possible to put a burner associated with an H ₂ quench located between the heat exchanger 47 and the heat exchanger 49 in order to bring a surplus of heat in the case where the heat supplied by the battery 11 is not enough to meet the needs.

Cooling system

This circuit is illustrated with reference to FIG. 13. In this FIG. 13, the parts in dotted lines refer to the hydrogen circuit H ₂ and to the primary air circuit previously detailed with reference to FIGS. 11 and 12. The cooling circuit a cooler gas also has the function of cooling the battery 11. It operates in a closed circuit to limit the need for compression.

The operation of the cooling circuit in destocking mode of a three flow system 10 is described below. The hot flow F _C haud exits the fuel cell 11 is then cooled through a heat exchanger 90 of the type / gas by the incoming fluid _F trating in the fuel cell 11. Then, the flow through yet another heat exchanger 91 forming heat recovery, in charge of recovering heat through a heat transfer fluid FC.

The flow is then completely cooled through another heat exchanger 92 of the gas / gas type by the recompressed fluid lcc printed in order to fight against the pressure drops of the circuit, then it still passes through an over-cooling device 93 before being compressed by the compression pump 94. Then, the compressed gaseous fluid is preheated by the outlet flow of the stack 11 at the level of the heat exchangers 92 and 90 before being injected into the fuel cell 11.

It should be noted that the fluid used as the third channel F3 can be any non-condensable gas in the temperature and pressure ranges of the process under consideration. It must also be non-corrosive to the different process materials with which it is in contact. Air may preferentially be chosen to fulfill these conditions, which furthermore has the advantage of not requiring any particular storage.

It should also be noted that the third channel F3 can either represent a heat exchanger integrated in the stack, similar to the patent application GB 2 151 840 A, or the enclosure containing the stacks in the case where one uses stacks optimized for exchange with the convective exchange enclosure, similarly to the patent application US 2006/105213 Al or radiative, similar to the international application WO 2013/060869 A1.

The system 10 can additionally comprise a fluid reservoir, when it does not correspond to air, a compressor making it possible to add fluid to the correct pressure in the loop in the event of an increase in the flow rate required by the system 10, and a purge valve to the fluid reservoir, to reduce the flow of coolant in the loop.

The system 10 can also, when the coolant is air, comprise a compressor for adding air to the correct pressure in the loop in the event of an increase in the heat transfer fluid flow rate required by the system 10, and a purge valve to the atmosphere, to reduce the flow of cooling air in the loop.

Moreover, in the case of the need for additional heat to be recovered on the high temperature heat exchangers 31, 49 and 91, a part of the hydrogen coming from the hydride tank 12 can be mixed with the primary cycle air as oxidant to be burned in a combustion chamber located upstream of the exchanger considered. Advantageously, the three-flow system allows the production of electricity, potentially carbon-free and / or renewable depending on the origin of the electricity used to produce the hydrogen. In addition, it allows the production of heat, required for the desorption of hydrogen in the hydride reservoir 12, with the possibility of burning a little hydrogen if the fuel cell 11 does not provide enough of it. herself. This eliminates the need for a high temperature heat source outside the system 10. In addition, it allows a range of electric power and / or achievable thermal that is wide around the nominal (45-105% in the example described here) .

Finally, although we obtain a lower yield compared to an air recirculation system, described above, because of the compression of the cathode air which increases the consumption of the compressors, this solution does not require storage. oxygen. It also allows a better maximum current density due to the greater maximum air flow (cathode air and heat transfer fluid) which ensures better cooling of the system.

Example of realization

An exemplary embodiment of a SOFC fuel cell 11 thermally coupled to a hydride reservoir 12 in destocking mode with a three flow system will now be described. The different values given in the following example are derived from simulations carried out on ProsimPlus software from thermodynamic models of cell cells as well as auxiliaries (pumps, converters, etc.). The purpose of the system 10 of this example is to provide electricity with high efficiency and wide power range. The storage of the hydrides in the hydride reservoir 12 is at a pressure of 10 bars. The power generation power range is between 28 and 68 kW AC for the grid, ranging from 33.5 to 77.6 kW for fuel cell 11 (with a PCI yield of 83% for operation at minimum power at 63% for its operation at maximum power), and the range of efficiencies obtained is between 50 and 54% PCI (lower calorific value of the introduced hydrogen). An H ₂ burner is used in addition for the desorption heat. The cooling fluid chosen is air. The system 10 thus comprises a magnesium hydride MgH ₂ hydride hydrogen storage at a pressure of 10 bars and at 380 ° C., consuming 75 kJ per mole of H ₂ released. The heat recovered on the exchangers is used to desorb the hydrogen, as well as to mitigate the heat losses on the process. The hydride reservoir 12 requires the provision of a desorption energy equal to 75 kJ / (mole of desorbed H ₂ ) and a temperature greater than 380 ° C. By taking into account the nip in the high temperature exchangers, only the heat of the process above 400 ° C can be recovered for this purpose. It is also taken into account heat losses on the process, the stack 11 and the tank 12, 2.7 kW to compensate.

In the event of a lack of heat recovered on the exchangers, part of the desorbed hydrogen is burned upstream of the heat exchanger forming heat recovery of the primary air circuit.

The flow rates of the different fluids were set as follows: for hydrogen H ₂ , the flow rate is constant and set at 12 NmL / min / (cm ² of cell); for primary air, the maximum flow rate is 17 NmL / min / (cm ² of cell); and for the cooling air, the flow rate is between 0 and 48 NmL / min / (cm ² of cell).

Moreover, the cooling strategy is as follows: the temperature of the hydrogen entering the cell 11 is constant and equal to 700 ° C .; the temperature of the primary air and cooling entering the cell 11 is constant and equal to 600 ° C; the stack outlet temperature is kept constant and equal to 850 ° C; at low power, the cooling air flow is turned off, and the primary air flow is adjusted to obtain the correct outlet temperature of the cell; when the power increases, the primary air flow is increased to reach 17 NmL / min / (cm ² of cell), and the primary air flow is then increased to a maximum flow of 48 NmL / min. / (cm ² of cell).

The results obtained are graphically represented in FIG. 14, which shows the evolution of the primary air flow rate D _a primary air and cooling air air cooling, expressed in NmL / min / (cm ² of cell), as a function of the net electric power (AC) P of the process, expressed in kW, and also in FIG. 15, which shows the evolution of the electric efficiency R of the process, expressed in percentages, in a function of the net power (AC) P of the process, expressed in kW, and finally on figure 16, which shows the evolution of the consumption CH2 in dihydrogen, expressed in kg / h, as a function of the net power P of the process , expressed in kW. In this figure 16, the curve Ca represents the total consumption in H ₂ , and the curve Cb represents the consumption of burned H ₂ for additional heat.

The net power P of the process is defined as the electrical output of the battery 11 and the associated turbine (primary air circuit) to which the consumption of compressors and recirculators is deducted. The whole is counted at the exit of the system, thus in power AC.

The electrical efficiency R of the process is defined as follows:

R = Net electrical power of the process P / [PCI H ₂ * Flow rate of H ₂ consumed]

The net process power corresponds to the production of the battery and the turbine, to which are subtracted the consumptions of the system, namely those of the compressors, the cold utilities and the power electronics.

The system 10 offers a wide range of power, because considering the optimum efficiency as nominal (54.12% to 63.9 net kW electric), we obtain a range in usable power ranging from 44 to 106% of the nominal.

The process is thus able to take advantage of the storage of the hydride reservoir 12, which has as a strong point a high density of hydrogen storage (on MgH ₂ type hydride, the mass of 5% by weight of hydrogen is reached. ), without external heat input to desorb hydrogen, which a more conventional system, such as a low temperature battery system (PEM, etc.) can not do.

It should be noted that for the recirculating air systems and three flows described above, the hydrogen utilization rate H ₂ (fraction of the incoming hydrogen consumed by the cell 11) is preferably less than 80%. so as to limit the degradation of the cells of the cell 11. In addition, the air flow rate is preferably chosen so that the oxygen content 0 ₂ at the fuel cell outlet 11 is at least 10%. If there is a need for significant cooling, the airflow can be increased up to a maximum of about 48 N mL / min / (cm ² of cell) on average. Moreover, for both recirculating air systems and three flows, the system 10 to meet the fluctuating electrical power requirements for the choice of H ₂ dihydrogen flow rate can be carried out in three main ways on the hydrogen circuit H ₂ , namely:

a constant utilization rate: the hydrogen flowrate is adjusted in such a way that the fraction of hydrogen consumed remains constant. This configuration is limited by the maximum flow rate of the different gases (hydrogen, air and cooling fluid) accepted by each channel of the fuel cell;

- Constant hydrogen flow rate H ₂ : the flow of hydrogen entering the fuel cell is kept constant, which has the effect of increasing the rate of use with the increase in power. This configuration is limited by the maximum rate of use allowed by the cell to limit the damage;

- Hydrogen flow rate H ₂ and variable power: the system modifies both the flow of hydrogen entering the cell and the fraction that is consumed. This configuration requires extensive control, especially on the flow of air and coolant, but offers a wider range of power response than the two modes shown above.

As for the choice of the primary air flow, it depends directly on the regime used. It is preferably maintained so as to keep the temperature rise relatively constant, and below 150 ° C. The air flow must also ensure the supply of oxygen, and is expected not to fall below the 10% oxygen output of the fuel cell.

As for the choice of coolant flow rate for a three flow system, it is adjusted to maintain the temperature rise in the fuel cell below maximum warming.

Furthermore, in the examples described above relating to the destocking mode, the additional heat necessary to desorb the hydrogen, which can not be provided by simple recovery, is ensured by burning a portion of the hydrogen. It is also possible to envisage a contribution by electric heating, even if the electricity can be a high price when operating in destocking mode, and that it will impact the performance of the system.

In addition, the system 10 can operate in a degraded mode. In particular, in storage mode, the hydrogen produced can be used for other uses than for storage in the hydride reservoir 12. This, however, requires a heat source to effect the vaporization of the water and to compensate the absence of heat provided by the reservoir which does not absorb the hydrogen produced. It can be an electrical source, resulting in a sharp decline in the efficiency of the system, or external, resulting for example from a subsidiary process. In destocking mode, in case of depletion of the hydride reservoir 12, it is possible to use another source of hydrogen, for example by pressure or liquid storage. We then have an excess of heat which must be evacuated. It can be removed from the system, for example by injection into an urban heat network, by use by a third party system, among others, or even be eliminated by the process, in which case there is need for an additional cooling system , for example an air cooler.

On the other hand, in the three flow system presented above, the cathode air operates in an open cycle to provide the oxygen necessary for the reaction. However, it is possible to operate with an air recirculation, similar to that described for the recirculating air system. This would reduce the air compression work on the cathode side, and thus slightly increase the efficiency. This would also make it possible to work at a higher current density than that obtained in the two systems envisaged, the flow rate of cooling fluid then going to double 48 NmL / min / (cm ² of cell). However, this would require oxygen storage, to ensure the complement of that consumed by the reaction at the cathode.

If we look at the electrical storage efficiency of the plant, represented by a complete storage cycle (87% optimum efficiency of conversion to electricity absorbed (ICP)), followed by a complete destocking cycle (optimal efficiency) hydrogen conversion rate absorbed to electricity of 54% in the case of a 3-flow system, and 60% in the case of an air recirculation system), which corresponds to the efficiency of the installation used for storage of electricity. energy, we achieves electricity storage efficiencies of 47% (3-stream system) and 52% (recirculating air system). This is greater than the efficiency that can be expected from a low temperature storage chain (composed of a PEM or alkaline electrolyser, and a PEM cell) which displays around 20% system efficiency.

Of course, the invention is not limited to the embodiments which have just been described. Various modifications may be made by the skilled person.

The invention has applications in several technical fields of industry, and mainly for the storage of electrical energy in the form of hydrogen. The sizing of the system 10, and in particular of the electrolyser 11 and the hydride reservoir 12, is then carried out according to the needs in terms of the power returned and the available electricity resources.

The system 10 can advantageously be coupled with renewable energies, for example of the photovoltaic and / or wind type, in order to provide a guarantee of electricity production. Then, a network injection profile can be realized, by producing electricity when the initial source of renewable energy production is too low, for example at night for photovoltaic, and storing it in the form of hydrogen when an excess of production manifests itself.

It is possible to design a system 10 dedicated to the production of hydrogen absorbed on hydrides, with replacement of the tank 12 when it is full, but still having the possibility of producing electricity, when for example the price Electricity in a conventional market is high.

Moreover, the storage and retrieval methods described above can be used independently and for different applications. For example, hydrogen stored on hydrides is a mode of transport of hydrogen. It is therefore possible through this process to supply hydrogen consumers with an integrated and efficient production process, the destocking of hydrogen on a customer site can then benefit from external heat inputs, such as fatal heat.

Claims

1. System (10) reversible electrolysis of water at high temperature, characterized in that it comprises:

a high temperature reversible electrolyser device (11), configured to operate in a SOEC-type solid oxide electrolyser mode, for the production of hydrogen and thus the storage of electricity, and / or in a stack mode with solid oxide fuel of the SOFC type, for the consumption of hydrogen and thus the destocking of electricity, said reversible electrolyser (11) being configured to operate at a pressure of between 8 and 12 bar,

a hydride reservoir (12), thermally coupled with said reversible electrolyser (11), configured to store the hydrogen in hydride form in solid-state electrolyser mode of the SOEC type of said reversible electrolyser (11) and / or to release hydrogen in SOFC solid oxide fuel cell mode of said reversible electrolyser (11),

the system (10) being configured to allow, when the reversible electrolyser (11) is configured to operate in a SOEC type solid oxide electrolyser mode, recovery of the heat released by the hydride reservoir (11) during the absorption of hydrogen to produce the pressurized water vapor to enter the reversible electrolyser (11), and to allow, when the reversible electrolyser (11) is configured to operate according to a SOFC solid oxide fuel cell, a recovery of the heat released by the outflow (s) of the reversible electrolyser (11) to allow the desorption of hydrogen from the hydride reservoir (12).

2. System according to claim 1, characterized in that the reversible electrolyser (11) comprises a stack of electrochemical cells (C1, C2) elementary solid oxides each formed of a cathode (2.1, 2.2), an anode (4.2) and an electrolyte (3.2) interposed between the cathode and the anode, and a plurality electrical and fluidic interconnectors (5) each arranged between two adjacent elementary cells.

3. System according to claim 1 or 2, characterized in that the reversible electrolyser (11) is configured to operate in a SOEC solid oxide electrolyser mode, and in that the system (10) then comprises:

a steam generator (18) for producing water vapor for the reversible electrolyser (11) by means of the heat released by the hydride reservoir (12), absorption of hydrogen, and supplied to the steam generator (18) via a coolant (FC).

4. System according to claim 3, characterized in that it further comprises:

one or more heat exchangers (16, 17, 20, 21) for preheating the inlet water (H ₂ O _to tai) of the system (10) and / or superheating of the incoming water vapor in the reversible electrolyser (11), via the flows of hydrogen (H ₂ ) and oxygen (O ₂ ) leaving the reversible electrolyser (11).

5. System according to claim 4, characterized in that it comprises heat exchangers (16, 17, 20, 21) upstream and downstream of the steam generator (18) to respectively allow the preheating of the water (H ₂ O _to tai) from the system (10) and the superheating of the water vapor entering the reversible electrolyser (11), via the hydrogen (H ₂ ) and oxygen (0 ₂ ) leaving the reversible electrolyser (11).

6. System according to any one of claims 3 to 5, characterized in that it further comprises:

a condenser (23), coupled to a phase separator (13), for receiving the unreacted water vapor in the reversible electrolyser (11) and the dihydrogen (H2) produced by the reversible electrolyzer (11) and condensing the unreacted water (l-hOrécup) to allow its recycling within the system (10).

7. System according to any one of claims 3 to 6, characterized in that it further comprises:

- A compression pump (14) for compressing the inlet water (l-hototai) of the system (10) to a pressure of between 2 and 15 bar.

8. System according to any one of claims 3 to 7, characterized in that it further comprises:

- An electric heater (22) upstream of the reversible electrolyser (11), providing additional superheating of water vapor, in particular up to 800 ° C.

9. System according to any one of claims 6 to 8, characterized in that it further comprises:

a dryer (24), upstream of the hydride reservoir (12) and downstream of the phase separator (13), designed to allow the humidity contained in the hydrogen (H ₂ ) to be removed before storage in the storage tank; hydrides (12).

10. System according to claim 1 or 2, characterized in that the reversible electrolyser (11) is configured to operate in a solid oxide fuel cell mode of SOFC type under pressure, and in that the system (10) then comprises:

at least one heat exchanger (30, 38, 47, 90) for preheating at least one flow entering the reversible electrolyser (11) via at least one flow leaving the reversible electrolyser (11); ).

11. System according to claim 1 or 2 or claim 10, characterized in that the reversible electrolyser (11) is configured to operate according to a solid oxide fuel cell mode of the SOFC type, and in that the system (10) then comprises:

at least one heat exchanger (31, 39, 49, 91) for recovering high temperature heat from at least one flow leaving the reversible electrolyser (11) via at least one fluid coolant (FC), in particular to allow the desorption of hydrogen from the hydride reservoir (12).

System according to claim 1 or 2, characterized in that the reversible electrolyser (11) is configured to operate in a solid oxide fuel cell mode of the SOFC type, and in that the system (10) is type "recirculating compressed air system" consisting of a hydrogen circuit and a primary air circuit.

13. System according to claim 1 or 2, characterized in that the reversible electrolyser (11) is configured to operate in a SOFC solid oxide fuel cell mode, and in that the system (10) is "Three flow system" type, consisting of a hydrogen circuit, a primary air circuit and a cooling circuit using a "three flow" type interconnector (5).

14. System according to claim 12 or 13, characterized in that the dihydrogen circuit comprises:

means for mixing (M1) hydrogen from the hydride reservoir (12) with the total recycling of hydrogen (H ₂ residuei) not consumed in the reversible electrolyser (11) over a pressure range of 2 to 15 bars,

- a heat exchanger (30) for preheating the incoming hydrogen flow (H _2t otai) in the reversible electrolyser (11) via the outgoing hydrogen flux (H ₂ ) of the reversible electrolyser (11) ,

a heat recovery heat exchanger (31) for recovering heat from the outgoing hydrogen flow (H ₂ ) from the reversible electrolyser (11) via at least one coolant (FC) ).

15. System according to claim 14, characterized in that it further comprises a heat exchanger (33) for cooling the flow of outgoing hydrogen (H ₂ ) from the heat exchanger (31), forming a recovery device. heat, by the flow of hydrogen (H ₂ ) out of a phase separator (34), allowing the recovery of the produced water.

16. System according to claim 12, characterized in that the primary air circuit comprises:

a heat exchanger (38) for preheating the flow of air entering the reversible electrolyser (11) via the air flow leaving the reversible electrolyser (11),

a heat exchanger (39) forming a heat recovery device for recovering high temperature heat from the air flow leaving the reversible electrolyser (11) via at least one coolant (FC) .

17. System according to claim 16, characterized in that it further comprises mixing means (Ml) of the air flow leaving the heat exchanger.

(39), forming heat recovery, with a complement of oxygen (Fo ₂ ) forming a total flow of air entering the reversible electrolyser (11).

18. System according to claim 17, characterized in that it further comprises:

- a heat exchanger (40) and a cooling device (41), for cooling the total flow of air mixed by the mixing means (Ml),

a compression pump (42) for compressing the air leaving the cooling device (41) before injection into the heat exchanger

(40) for preheating.

19. System according to claim 13, characterized in that the primary air circuit comprises:

a heat exchanger (47) for preheating the flow of air entering the reversible electrolyser (11) via the air flow leaving the reversible electrolyser (11),

- A heat exchanger (49), heat recovery, for recovering heat from the air flow leaving the reversible electrolyser (11) through at least one heat transfer fluid (FC).

20. System according to claim 13, characterized in that the cooling circuit comprises:

a heat exchanger (90) for preheating the incoming flow (Fentram) in the reversible electrolyser (11) via the hot flow (F _C hd) leaving the reversible electrolyser (11),

a heat exchanger (91), forming a heat recovery device, for recovering heat from the hot stream (F _C Hout) leaving the reversible electrolyser (11) via at least one coolant (FC) )

- a heat exchanger (92) and an overcooling device (93) for cooling the hot flow (F _{C out} ) leaving the heat exchanger (91),

a compression pump (94) for compressing the flow exiting the heat exchanger (92) and the supercooling device (93) to form a compressed fluid flow (Fcompnmé) for cooling the hot flow; (F _C hout) exiting the heat exchanger (92).

21. A method of storage and / or retrieval of electricity by reversible electrolysis of water at high temperature, characterized in that it is implemented by means of a reversible electrolysis system (10) of the high temperature water according to any one of the preceding claims, and in that it comprises the steps of: when the reversible electrolyser (11) under pressure operates in a solid oxide electrolyser mode of the SO EC type, recovery of the heat released by the hydride reservoir (12) during the absorption of hydrogen for producing the pressurized water vapor for entering the reversible electrolyser (11), and

when the reversible electrolyser (11) under pressure is configured to operate in a solid oxide fuel cell mode of the SOFC type, recovery of the heat released by the outflow (s) of the reversible electrolyser (11) to enable the desorption of hydrogen from the hydride reservoir (12).

22. The method as claimed in claim 21, characterized in that it is implemented according to a storage mode of electricity, the high temperature reversible electrolyser (11) being configured to operate in a solid oxide electrolyser mode. SOEC type, and the method comprising the step of performing the high temperature electrolysis reaction of water vapor to produce hydrogen and thus store electricity.

23. The method of claim 22, characterized in that it is implemented by means of a system (10) reversible electrolysis of water at high temperature according to claims 5, 6 and 7, and in that it comprises the following successive steps:

- introduction of the total water (H ₂ O _to tai) of the system (10), comprising injection water (H ₂ 0) and recycled water (H ₂ O _r ecup) from the separator of phases (13) in the compression pump (14) to a pressure of between 2 and 15 bar,

- circulation of the total water (H ₂ O _to tai) of the system (10) through heat exchangers (16, 17) to allow preheating of the inlet water

(HhOtotai) of the system (10) through the flows of hydrogen (H ₂ ) and oxygen (0 ₂ ) leaving the reversible electrolyzer (11),

- introducing the inlet water (H ₂ O _to tai) from the system (10) into the steam generator (18), to produce the pressurized water vapor for the reversible electrolyzer ( 11) through the heat generated by the hydride reservoir (12), during the absorption of hydrogen, and supplied to the steam generator (18) by a heat transfer fluid (FC),

- circulation of water vapor through heat exchangers (20, 21) to allow superheating of the water vapor before entering the reversible electrolyser (11), through the flow of hydrogen (H ₂ ) and oxygen (0 ₂ ) leaving the reversible electrolyser (11),

- additional superheating of the steam to reach the working temperature of the electrolyser (11) using an electric heater,

- introduction of water vapor under pressure in the reversible electrolyzer (11) for the production of hydrogen (H ₂ ) and oxygen (O ₂ ) streams,

- cooling the flow of hydrogen (H ₂ ) and oxygen (0 ₂ ) through the heat exchangers (16, 17, 20, 21),

- condensation of the unreacted water vapor under pressure in the phase separator (13) to produce recycle water (H ₂ O _r ecu _P ) reintroduced into the system (10),

- Storage of hydrogen (H ₂ ) dried product in the hydride tank (12).

24. The method of claim 21, characterized in that it is implemented according to an electricity destocking mode, the high temperature reversible electrolyser (11) being configured to operate in a solid oxide fuel cell mode. SOFC type, and the method comprising the step of performing the reverse reaction of high temperature electrolysis of water vapor to destock hydrogen and thereby produce electricity.

25. The method of claim 24, characterized in that it is implemented by means of a system (10) of reversible electrolysis of water at high temperature of the type "recirculating compressed air system" according to claim 12, the system (10) being further according to claims 14 to 18, and comprising the following successive steps: • for the dihydrogen circuit (H ₂ ):

mixing hydrogen from the hydride reservoir (12) with the total recycling of hydrogen (1-h siduei) not consumed in the reversible electrolyzer (11) via the mixing means (M1),

- injection of total hydrogen (H _2t otai) through the heat exchanger (30) allowing its preheating by the outgoing hydrogen flow (H ₂ ) of the reversible electrolyzer (11),

injection of total hydrogen (H _2t otai) into the reversible electrolyser (11) for its consumption and the production of water, electricity and heat,

cooling the hydrogen flow leaving the reversible electrolyser (11) by the preheating heat exchanger (30),

- Cooling the hydrogen flow exiting the heat exchanger (30) preheating by the heat exchanger heat exchanger (31), for recovering the heat by exchanging it with a coolant (FC) ,

- separating the stream of hydrogen (H _2r ésiduei) and the flow of water produced after the phase separator (34),

- recycling of unused hydrogen by recompressing only the value of the losses,

• for the primary air circuit:

injecting the air leaving the reversible electrolyser (11) through the cooling heat exchanger (38) to be cooled by the compressed air entering the reversible electrolyser (11),

- Injection of the air leaving the heat exchanger (38) cooling through the heat exchanger (39), forming heat recovery, traversed by a heat transfer fluid (FC),

mixing the air leaving the heat exchanger (39), forming a heat recovery device, by mixing means (M1) with a complementary compressed oxygen flow (F02),

injecting this mixture into a heat exchanger (40), then a cooling device (41), then a compression pump (42) to compensate the pressure drops and to obtain compressed air injected into this cooling heat exchanger (40) downstream of the mixing means (M1),

- Injecting the air from the heat exchanger (40) cooling in the heat exchanger (38) for its preheating, then injection into the reversible electrolyser (11) at the targeted pressure of 2 to 15 bar .

26. The method of claim 24, characterized in that it is implemented by means of a system (10) of reversible electrolysis under high temperature water pressure type "three flow system" according to the claim 13, the system (10) being further according to claims 14, 15, 19 and 20, and comprising the following successive steps:

• for the dihydrogen circuit (H ₂ ):

- hydrogen mixture from the hydride container (12) to the target pressure of 2 to 15 bars, with total recycling of hydrogen (H _2r ésiduei) unconsumed in the reversible electrolyzer (11) by the biasing means (Ml),

injection of total hydrogen (H _2to tai) at the targeted pressure of 2 to 15 bar through the heat exchanger (30) allowing its preheating by the outgoing hydrogen flow (H ₂ ) of the electrolyser reversible (11),

injection of total hydrogen (H _2to tai) at the targeted pressure of 2 to 15 bar in the reversible electrolyser (11) for its consumption and the production of water, electricity and heat,

- recycling of the unused hydrogen by recompressing only the value of the pressure losses of the assembly, • for the primary air circuit:

- ambient air injection (Fairi) in a compression pump (48) to a pressure of between 2 and 15 bar,

preheating the air entering the preheating heat exchanger (47) via the air flow leaving the reversible electrolyser (11),

injecting the preheated incoming air into the reversible electrolyser (11) at the target pressure,

cooling the air leaving the reversible electrolyser (11) in the preheating heat exchanger (47),

- cooling the air exiting the heat exchanger (47) preheating through the heat exchanger heat exchanger (49) to obtain heat through at least one heat transfer fluid (CF)

injecting the air exiting the heat exchanger (47), forming a heat recovery unit, into a gas turbine (43) before ejecting the outgoing air (F _a ir2),

· cooling system :

cooling of the hot flow (F _C Hout) leaving the reversible electrolyser (11) through the heat exchanger (90) for preheating by the incoming fluid (entering) in the reversible electrolyser (11),

cooling the flow exiting the heat exchanger (90) for preheating in the heat exchanger (91), forming a heat recovery device, by means of at least one coolant (FC),

total cooling of the flow exiting the heat exchanger heat exchanger (91) in a heat exchanger (92) by the recompressed fluid flow (compressed,

- injection of the flow exiting the heat exchanger (92) traversed by the recompressed fluid flow (Fcompnmé) in an overcooling device (93), then a compression pump (94),

- Preheating the flow exiting the compression pump (94) by the flow leaving the reversible electrolyzer (11) before entering the reversible electrolyser (11) at the target pressure of 2 to 15 bar, especially 8 to 12 bars.