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    • 专利摘要:
    The invention relates to a thermal management method of a system for storing energy and the cogeneration of electricity and heat, and to this system. The system comprises a fuel cell capable of producing electricity and heat in an exothermic reaction and producing hydrogen in an endothermic reaction. The system also includes a hydrogen storage and delivery device, comprising a material configured to generate heat upon storage of hydrogen and to release hydrogen in the presence of heat. When the fuel cell operates according to the endothermic reaction, liberated hydrogen is conveyed to the material. The heat from the material is conveyed to a source of water to bring it to a predetermined temperature. The fuel cell receives this water and electricity for a hydrolysis reaction.
    公开号:FR3033943A1
    申请号:FR1552272
    申请日:2015-03-19
    公开日:2016-09-23
    发明作者:Annabelle Brisse；Qingxi Fu
    申请人:Electricite de France SA；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The invention relates to the field of thermal management of systems for the cogeneration of electricity and heat. The invention also relates to a system for energy storage and the cogeneration of electricity and heat to which the method can be applied. The system in question comprises in particular a fuel cell operating with hydrogen.
    [0002] TECHNOLOGICAL BACKGROUND The development of renewable energy sources is accompanied by the development of technologies that optimize their use and their yields. Among the various sources of renewable energy available, fuel cells, capable of generating electricity while limiting the emission of greenhouse gases, are of great interest. Fuel cells are electrochemical devices whose operation relies on chemical oxidation-reduction reactions to produce electricity: an oxidation of a reducing fuel on one electrode and a reduction of an oxidant on another electrode.
    [0003] Hydrogen fuel cells can in particular operate according to two chemical reactions, depending on whether the fuel cell is in the electrolysis regime or in the discharge regime. Hydrogen fuel cells can operate in a variety of chemical reactions involving, for example, oxygen, methanol, methane, or simply dihydrogen. For simplicity, the case of fuel cells involving oxygen and hydrogen will be referred to. A first exothermic reaction allows the fuel cell to produce electricity and heat by recombination of dihydrogen and oxygen: H2 ± 1/202 -> H2O + 2e- + Q exothermic reaction (discharge) 3033943 2 A second endothermic reaction allows to perform electrolysis with a fuel cell and to produce hydrogen and oxygen, by means of a supply of energy in the form of electricity and heat: H20 + Q + 2e-> H2 ± 1/202 endothermic reaction ( Electrolysis) The heat Q and electricity required for the endothermic reaction to produce hydrogen at a given temperature and pressure depend in part on the power supply used to effect the electrolysis. The electrical voltage applied to the fuel cell in the electrolysis regime indeed makes it possible to define three different modes of operation: allothermal, autothermal or exothermic.
    [0004] The autothermal mode corresponds to a mode in which the only power supply makes it possible to supply all the energy necessary for the endothermic reaction, that is to say that the quantity of energy Q consumed by the endothermic reaction is fully offset by the supply of electrical energy. The voltage applied to an autothermically charged fuel cell is called a thermoneutral. The allothermal mode corresponds to an applied voltage lower than the thermoneutral voltage. This mode seems a priori interesting because it involves a lower power consumption. However, it assumes an external heat input into the fuel cell which is capable of introducing temperature gradients detrimental to the integrity of the cell. Moreover, in the case of hydrolysis, the allothermal mode has the drawback of providing a lower water-to-hydrogen conversion efficiency than autothermal mode because the endothermic reaction is limited by the quantity of electrons available for hydrolysis. The only way to compensate for this deficit is to increase the cell size of an electrochemical cell, which does not prove to be an ergonomic solution. The exothermic mode corresponds to a voltage greater than the thermoneutral voltage. For such voltage values, the energy input in electrical form is such that it produces by itself more heat than necessary in the endothermic reaction. This mode consumes more electrical energy but ensures a good conversion efficiency without requiring an increase in cell size. In contrast, it induces temperature variations within the fuel cell that can affect its structural integrity. These different modes of operation depending on the control of the electrolysis in a fuel cell require a thermal management and more particularly energetic 5 particular. Hydrogen and oxygen fuel cells have the advantage of not emitting greenhouse gases. One of the disadvantages of their operation lies in the fact that the electrolysis and discharge reactions have a very different thermodynamic behavior: one produces electricity and heat and requires a supply of gaseous reactants, the other consumes electricity and heat. and produces a release of gas. Therefore, in order to manage the flow of reagents, products, electricity and heat, special thermal management is required. The problem of hydrogen transport is advantageously solved by providing a device for storing the hydrogen produced during the endothermic reaction in order to return it as a reagent for supplying the fuel cell in the discharge regime. Several technical solutions for storing hydrogen and then restoring it are possible. The document WO2013 / 190024 proposes a device allowing the reversible storage by adsorption of hydrogen in a material. When hydrogen is stored in the material, heat is released; the stored hydrogen can then be released by applying heat to the material. In addition to the storage device proposed in WO2013 / 190024, other storage devices may be used, for example devices in which the material may be stored under pressure in cylinders or cylinders.
    [0005] The reversible hydrogen storage device of WO2013 / 190024 makes it possible to optimize the flow of material from and to the fuel cell by means of connections between the fuel cell and the reversible storage device. However, such a system does not achieve energy yields typically greater than values between 30% and 50%. This low overall efficiency can be attributed to non-upgraded heat losses that occur in the operation of such a system such as, for example: heat dissipation when storing hydrogen in the material, ohmic losses in the cell fuel, or the energy required to perform the electrolysis and release hydrogen from the material. Therefore, a method of thermal management of a system comprising a fuel cell and a device for storing and releasing hydrogen in a material which makes it possible to increase the overall energy efficiency of the system is sought. A system whose characteristics allow an increase in overall energy efficiency is also sought. SUMMARY OF THE INVENTION In order to meet the problems set out above, the present invention proposes a method of thermal management of a system for storing energy and for co-generating electricity and heat, in which the system comprises a fuel cell capable of producing electricity and heat according to a first exothermic reaction by recombination of oxygen and of a compound based on hydrogen and capable of producing hydrogen-based compound according to a second endothermic reaction by decomposing a fluid comprising hydrogen; a hydrogen storage and release device comprising a material configured to generate heat upon storage of the hydrogen-based compound and releasing the compound based on hydrogen in the presence of heat. The method comprises: when the fuel cell is operating according to the second endothermic reaction: - feeding the hydrogen-based compound released by the second endothermic reaction to the material that comprises the hydrogen storage and release device, thereby generating the heat ; conveying at least a portion of the heat from the material to a source of the fluid comprising hydrogen so that the fluid comprising hydrogen is brought to a predetermined temperature; and - supplying the fuel cell 30 with fluid at the predetermined temperature and with electricity for decomposing the fluid to a predetermined temperature, thereby generating the hydrogen-based compound to be stored in the device material. storage and release of hydrogen.
    [0006] The hydrogen-based compound employed in the process may be any hydrogen-based fuel present in a fuel cell. It is thus possible to mention by way of example: methanol, methane, or simply dihydrogen. For the sake of simplicity, reference will hereinafter be made to hydrogen as a hydrogen-based compound.
    [0007] The invention maximizes the energy produced in the form of heat during the storage of hydrogen in the material of the hydrogen storage and release device. The invention proposes to use the heat produced during storage of hydrogen in the material not to feed the endothermic reaction in the fuel cell but to carry a fluid comprising hydrogen at a predetermined temperature. The fluid in question serves to feed the fuel cell reagent for the endothermic reaction, for example water in the case of hydrolysis. This predetermined temperature is a function of the nature of the fuel cell used. Indeed, some fuel cells operate electrolysis at temperatures below 100 ° C while others are provided for electrolysis at a higher temperature, typically up to 1000 ° C. Unlike conventional approaches in optimizing the thermal management of a storage system of energy and co-generation of electricity and heat, the invention does not reuse the heat produced at the time of electrolysis to balance the endothermic reaction in the fuel cell. Because of the risk of damage to a fuel cell subjected to temperature gradients, many efforts are generally made to ensure that the battery receives all the heat required for the endothermic reaction to not alter the temperature. fixed and homogeneous reigning in the stack in the electrolysis regime. This desire to maintain the temperature in the fixed and homogeneous fuel cell is particularly present when the electrolysis is carried out in allothermal mode, which is more economical in electricity. The solution proposed by the present invention is therefore based on an original approach. The heat released by the material during hydrogen storage is recovered upstream of the fuel cell in a source of fluid used to supply the fuel cell with reagents. By bringing this fluid to the temperature that is intended for the endothermic reaction in the fuel cell, the invention avoids creating harmful temperature gradients in the cell, and avoids the need for an external heat source to heat the cell. fluid. The fluid supplying the reactant fuel cell can then act as a coolant and bring the stack efficiently to its electrolysis temperature without creating gradients. Indeed, the circulation of the fluid in the fuel cell makes it possible to ensure rapid heat transfer by convection and conduction. On the other hand, by routing heat to the outside of the fuel cell to heat a fluid, the invention provides some flexibility in the choice of operating temperature of the fuel cell, as far as the amount The amount of heat transferred to the fluid is adjustable to achieve any desired electrolysis temperature. The method of the invention makes it possible to increase the overall energy efficiency of the system to reach a yield of the order of 80%. Advantageously, the method may further comprise, when the fuel cell is operating according to the first exothermic reaction: - conveying at least a portion of the heat produced by the first exothermic reaction from the fuel cell to the material, thereby releasing the hydrogen-based compound stored in the material; and - feeding the hydrogen-based compound from the material to the fuel cell for feeding the first exothermic reaction. The use of a part of the heat produced by the exothermic reaction to release the hydrogen stored in the material also contributes to improving the overall energy efficiency of the system to a value of the order of 80%. Moreover, these flows of hydrogen and heat are in perfect agreement with the needs of the system: the hydrogen released by part of the heat of the endothermic reaction serves to supply the fuel cell in the discharge regime. Advantageously, the method may further comprise, when the fuel cell is operating according to the first exothermic reaction: - feeding at least a portion of the heat from the fuel cell to a cold source; and when the fuel cell operates according to the second endothermic reaction: - convey at least a portion of the heat from the material to the cold source.
    [0008] The use of the heat generated by the system can be used in any type of installation, for example for domestic heating. The cold source may for example be a heat exchanger or a hot water tank for domestic hot water. According to one embodiment, the method further comprises: heating the fluid to a predetermined temperature of between 300 ° C and 1000 ° C.
    [0009] The fluid comprising hydrogen may for example be water. By fixing the temperature at a value between 300 ° C. and 1000 ° C., the fluids used in fuel cells, in particular water, are in the vapor state. On the other hand, the electricity required to effect the endothermic reaction is reduced as the electrolysis temperature increases. According to one embodiment, the method further comprises: heating the fluid to a predetermined temperature of between 650 ° C and 850 ° C.
    [0010] A fluid temperature comprising hydrogen between 650 ° C and 850 ° C achieves an optimum overall energy efficiency in the system, particularly with solid ceramic oxide fuel cells. The amount of electrical energy required by the endothermic reaction is then lower and the heat required for the endothermic reaction can be efficiently provided by the fluid itself. According to an advantageous embodiment, the method further comprises: supplying the fuel cell with electricity from an energy source; and storing excess electricity from the energy source in the form of the hydrogen-based compound in the material of the hydrogen storage and delivery device by decomposing the fluid brought to the predetermined temperature in the fuel cell operating according to the second endothermic reaction.
    [0011] In doing so, the system to which the process is applied can work together with renewable energy sources or be connected to the electricity grid. The electrical energy can be stored as hydrogen during a consumption trough or a peak of electricity production, and later retrieved when needed. The invention also relates to a system for energy storage and the cogeneration of electricity and heat comprising: a fuel cell capable of producing electricity and heat in a first exothermic reaction by recombination of oxygen and hydrogen. a hydrogen-based compound capable of producing the hydrogen-based compound following a second endothermic reaction by decomposition of a fluid comprising hydrogen by consuming electricity and heat; a hydrogen storage and release device comprising a material configured to generate heat upon storage of the hydrogen-based compound, and releasing the hydrogen-based compound in the presence of heat. The system further comprises: a source of the fluid comprising hydrogen, said source being connected to the fuel cell, a first connection connecting the source of said fluid to the hydrogen storage and release device, said first connection being intended to convey heat generated during storage of the hydrogen-based compound in the material to the source of said fluid.
    [0012] A system having a connection for conveying heat released by the hydrogen storage and delivery device enables the method described above to be carried out. The source of fluid in question can be in various forms, such as a reservoir storing the fluid.
    [0013] According to one embodiment, the fuel cell is connected to the hydrogen storage and release device by: - a second connection for conveying the hydrogen-based compound released from the material to the fuel cell; and a third connection for conveying the heat generated in the fuel cell to the material. Such connections allow hydrogen to be conveyed from the fuel cell to the hydrogen storage and release device and vice versa. Furthermore, the heat generated during the exothermic reaction can be used to release the stored hydrogen to supply the fuel cell with reagent. According to one embodiment, the hydrogen storage and release device is configured to store the compound at hydrogen base at a pressure below 15 bar. By operating at low pressures below 15 bar, the system is less likely to explode, and does not require the use of complicated and expensive equipment for compression or liquefaction of hydrogen. The risk of explosion at high pressure results from the fact that hydrogen is a highly flammable compound. According to one embodiment, the material that comprises the hydrogen storage and release device comprises a metal hydride.
    [0014] Metal hydrides are particularly suitable materials for storing hydrogen directly by adsorption without resorting to a pressure storage tank. According to an advantageous embodiment, the metal hydride comprises magnesium hydride. More particularly, the metal hydride may be chosen from compounds of the magnesium family such as MgH2, NaMgH2, Mg2FeH6, Mg2NiH4.
    [0015] Magnesium hydride is particularly valuable because it has the greatest hydrogen adsorption capacity of all binary hydrides and generates a large amount of heat during the adsorption storage process. Thus, the use of this compound contributes to increasing the overall efficiency of the system by providing more exploitable energy.
    [0016] According to one embodiment, the fuel cell comprises a solid oxide ceramic cell.
    [0017] Fuel cells generally consist of a stack of elementary cells. The particular choice of solid oxide ceramic cells is motivated by the fact that such fuel cells are resistant to temperatures between 650 ° C and 850 ° C. By choosing to perform the electrolysis in the fuel cell at such temperatures, the electricity requirements of the endothermic reaction are reduced, which makes such operation particularly economical in electricity. Moreover, the heat consumed by the endothermic reaction can then be provided by the heated fluid, this heat constituting an important part of the energy consumed by the endothermic reaction.
    [0018] According to one embodiment, the solid oxide ceramic cell comprises a material selected from ionic conductive materials and protonic conductive materials. Proton conductive materials generally operate well at temperatures between 400 ° C and 600 ° C, while ionic conductive materials are suitable for temperatures between 650 ° C and 850 ° C. Another advantage in choosing these materials is that they do not require the use of noble materials acting as a catalyst in low temperature fuel cells. Fuel cells are then less expensive to produce.
    [0019] In particular, the ionic conductive material may be yttriated zirconia and the proton conductive material a barium, indium and titanium compound. According to one embodiment, a power source supplies the fuel cell.
    [0020] Advantageously, the energy source can be chosen from: a connection to an electrical network and a photovoltaic panel. DESCRIPTION OF THE FIGURES The method which is the subject of the invention will be better understood on reading the following description of exemplary embodiments presented for illustrative purposes, in no way limiting, and on the observation of the following drawings in which: Figure 1 is a diagrammatic representation of a system for the storage and co-generation of electricity and heat indicative of heat and material exchange in a discharge regime according to one embodiment of the invention; and FIG. 2 is a schematic representation of a system for the storage and co-generation of electricity and heat indicating the exchange of heat and material in the electrolysis mode according to one embodiment of the invention; and FIG. 3 is a graphical representation of the evolution, as a function of the operating temperature of a fuel cell in the electrolysis regime: free energy (Gibbs enthalpy), heat consumed by the fuel cell and the enthalpy of the endothermic reaction. For the sake of clarity, the dimensions of the various elements shown in these figures are not necessarily in proportion to their actual dimensions. In the figures, identical references correspond to identical elements. DETAILED DESCRIPTION The invention relates to an original method of thermal management of a system for energy storage and the cogeneration of electricity and heat. The method which is the subject of the invention involves a system as diagrammatically represented in FIGS. 1 and 2, comprising a fuel cell 1, operating according to two chemical reactions, one endothermic and the other exothermic, and a storage device. and hydrogen release 2. The fuel cell 1 generally consists of a plurality of elementary cells each comprising an anode and a cathode. In the so-called "fuel cell" or "discharge" regime represented by the word "SOFC" in FIG. 1, the fuel cell 1 produces electricity and heat by recombining a hydrogen-based compound with oxygen. Fig. 1 shows, by way of example, a hydrogen fuel cell, for which the hydrogen-based compound is hydrogen dihydrogen H 2. The invention can, however, quite be implemented on other categories of fuel cells using, as a hydrogen-based compound, other compounds such as, for example, methanol, or methane. Figure 1 schematically shows the configuration in which there is a system for energy storage and co-generation of electricity and heat when the fuel cell 1 produces electricity and heat. The hydrogen storage and release device 2 is typically in the form of an enclosure comprising a material capable of storing a compound based on hydrogen such as dihydrogen. In the embodiment described hereinafter, the hydrogen storage and delivery device 2 comprises as a material a metal hydride. The metal hydrides have the advantage of allowing a low pressure storage, typically less than 15 bars, of a large amount of hydrogen. Operation at low pressures reduces manufacturing and operating costs as well as the risk of explosion when using such a system. Indeed, most reversible hydrogen storage devices rely on the use of tanks requiring hydrogen compression or liquefaction, involving a higher operating cost. Hydrides of the magnesium family, including in particular MgH 2, NaMgH 2, Mg 2 FeH 6, Mg 2 NiH 4 are particularly interesting because of their high capacity for adsorbing hydrogen and the heat they release by releasing hydrogen. MgH2 is the metal hydride that has the highest hydrogen adsorption capacity of all binary hydrides. It also allows to generate a large amount of heat. The storage and release of hydrogen in magnesium hydride obeys the following reactions: MgH2 + 75 kJ / mol -> Mg + H2 Mg + H2 -> MgH2 + 75 kJ / mol These two reactions typically occur under pressure ambient temperature and for temperatures between 200 ° C and 500 ° C.
    [0021] The table below summarizes the properties of the various hydrides of the magnesium family that can be used: Amount AH (energy) Stored hydrogen storage temperature density provided by equilibrium storage (in ° C) (mass%) reaction ) heat at 1 bar pressure (kJ / mol H2) (kWh / kg) MgH2 7.7 75 0.78 280 NaMgH2 4.0 86 0.47 380 Mg2FeH6 5.5 77 0.55 320 Mg2NiH4 3.6 62 0.31 250 As shown schematically in Figure 1, the discharge regime The fuel cell 5 is supplied by a supply of O 2 oxygen via an air inlet 15 and a hydrogenation of hydrogen H 2 from the material to the fuel cell 1. The release of the stored hydrogen is effected at the same time. using the endothermic reaction described above by providing heat Q produced in the fuel cell 1 by the exothermic reaction of recombination of oxygen and hydrogen. The heat Q typically represents only a portion of the total heat produced by the fuel cell 1 in the discharge regime. Indeed, another part of the heat produced, corresponding to a heat Q ', is advantageously upgraded by being conveyed via a connection 12 to meet a need for energy at a cold source. The cold source may for example be domestic heating within an installation 4 15 such as a building.
    [0022] The electric energy produced by the fuel cell is also recovered by supplying the installation 4 with energy via an electrical connection 11. In the case of a fuel cell 1 with hydrogen, the exothermic reaction of the battery in discharge regime produces water. This water is advantageously recovered via a fluid circuit 13 to be stored in a tank 3. It should be noted that the system described above can not be completely closed. Thus, some of the energy produced in the fuel cell dissipates as lost heat Qp, ep. This heat Qp, ep is not valued in the system and results inter alia ohmic losses in the stack and losses by thermal conduction in the materials constituting the system. As shown in FIG. 1, the installation 4 can also be supplied with electrical energy via a power source 5 outside the system. This energy source can for example be a photovoltaic panel or an electrical network. The installation 4 is connected to this energy source by a connection 50.
    [0023] The operation of the system described above when the fuel cell operates in a discharge regime, that is to say according to a first exothermic reaction, has the advantage of optimizing the flow of hydrogen and heat between cells. fuel 1 and hydrogen storage and release device 2. By redirecting a portion of the Q heat produced in the fuel cell, the system eliminates an external source of heat to release the stored hydrogen. and ensure a continuous supply of the exothermic reaction in reagents. Figure 2 shows schematically the configuration of the same system as that described above when the fuel cell 1 operates according to the electrolysis regime, also called SOEC. In electrolysis, the fuel cell is the seat of a second endothermic reaction. In the case of a dihydrogen fuel cell, this endothermic reaction corresponds to the hydrolysis of water at a chosen temperature. Hydrolysis therefore involves a supply of H20 water, a source of electrical energy and a source of thermal energy.
    [0024] The electrolysis in the fuel cell 1 may advantageously be made by supplying electrical energy from the external power source 5 to the system via a connection 51. Depending on the type of fuel cell 1 used, the The temperature in the cells of the cell can typically vary between 20 ° C and 1000 ° C. The endothermic reaction consumes a fluid comprising hydrogen to decompose it into a hydrogen-based compound. In the case illustrated in FIG. 2, the fluid is water and the dihydrogen compound. The endothermic reaction produces oxygen, discharged to the outside of the system through an outlet 17, and dihydrogen, supplied to the energy storage and release device 2. Qs heat is produced during storage of hydrogen by adsorption in the material based on magnesium hydride storage device and hydrogen release 2. A conventional approach would be to reuse this heat to supply the fuel cell 1 in thermal energy. However, the invention proposes another use of this heat which is more economical and less expensive to implement. The invention does not propose to feed the endothermic reaction of the fuel cell directly into heat. A direct supply of heat, generally adopted in the thermal management of a system comprising a fuel cell, has several disadvantages. First, the cells of a fuel cell can tolerate temperature changes and are therefore exposed to an increased risk of structural degradations in the presence of temperature gradients. This constraint makes it difficult to closely control the flow of heat to the cell, especially since the heat requirements depend on the manner in which the electrical energy is supplied to the fuel cell, depending on whether the electrolysis mode is allothermal. autothermic or exothermic. As shown in FIG. 2, the system of the invention carries the heat Qs via a first connection 22 to a source 6 of the fluid comprising hydrogen. In the case shown in Figure 2, the source 6 comprises water. This source is carried, thanks to the heat from the hydrogen storage and release device 2 at a predetermined temperature Tc. Advantageously, this predetermined temperature is chosen to correspond to a temperature T prevailing in the fuel cell during the electrolysis regime. It is preferred to choose a predetermined temperature higher than the temperature prevailing in the fuel cell 1 so that the fluid brought to the predetermined temperature 60, in this case water, can itself provide the necessary heat. to the endothermic reaction and to compensate for any heat loss in the fluid circuit connecting the water source 6 to the cell. The source 6 may be part of a closed fluidic circuit incorporating the water reservoir 3, and connections allowing the flow of fluid between the reservoir and the fuel cell 1.
    [0025] The heat Qs may not correspond to all the thermal energy generated by the hydrogen adsorbent material. In such a case, and as shown in FIG. 2, the resulting heat fraction Q "generated by the material during the hydrogen adsorption can be upgraded by being supplied to the plant 4. Thermal losses Q'p can occur in the fluidic circuit carrying water to the cell, as well as in a connection connecting the hydrogen storage and release device 2 to the plant 4. The use of water brought to a predetermined temperature Tc assures a simple and efficient thermal management in the system, since the heat released by the hydride during hydrogen storage is used to vaporize the water entering the cell in the electrolysis regime. the operating temperature of the electrolyser via the recovery of the heat of the exit gases (in this case oxygen and hydrogen) which can be recovered by means of high temperature heat exchangers. As soon as the ceramic cell is heated directly, the water vapor acts as a heat transfer fluid capable of smoothing a temperature gradient in the fuel cell in the electrolysis regime. The circulation of the fluid makes it possible to maintain the endothermic reaction at a stable temperature and chosen by the quantity of heat Qs supplied to the source 6. As will be discussed hereinafter, the choice of the predetermined temperature Tc at which the water is carried is depends partly on the nature of the fuel cell 1 used and a choice of thermal management favoring electrical consumption or thermal consumption. The heat input provided by the superheated steam makes it possible to reduce the electrical consumption of the electrolysis reaction by maintaining the device under autothermic or even allothermal conditions. As indicated in FIG. 2, the fuel cell in the electrolysis regime is also the seat of energy losses 18, typically by ohmic losses E.
    [0026] FIGS. 1 and 2 show two configurations in which there is a system for energy storage and co-generation of electricity and heat depending on whether the fuel cell 1 is in the electrolysis regime (FIG. 2) or in the operating mode discharge (Figure 1). The system described above thus comprises, in addition to a fuel cell 1, a hydrogen storage and release device 2 and a source 6 of water: a first connection 22 for conveying heat Qs towards the source 6, a second connection 20 for ensuring a flow of hydrogen between the fuel cell 1 and the hydrogen storage and release device 2, and a third connection 10 for conveying heat Q from the battery to fuel 1 to the storage device and release of hydrogen 2 in the discharge regime.
    [0027] The various flows of electricity, heat and material between the various constituents of the system described above are part of a process that is the subject of the present invention. The method of the invention consists in particular in conveying the heat Qs produced in the hydrogen storage and release device in order to bring the water from the source 6 to the desired predetermined temperature Tc, as already described above.
    [0028] The combined use of an external power source and a system for energy storage and the cogeneration of electricity and heat makes it possible to smooth the fluctuations in the consumption of electrical energy in an electricity grid. any size. Indeed, the power source 5 may not permanently produce the amount of energy that the installation 4 needs. A photovoltaic panel thus produces electricity only under certain lighting conditions which do not systematically correspond to the needs of consumption. The system described above thus makes it possible to store in the form of hydrogen any excess energy produced and then to restore it when the energy demand exceeds the energy production. Used in a larger power grid, such a system makes it possible to smooth the consumption curves and thus simplify the management of the electricity network in view of safer energy production, less subject to power cuts. Sudden peaks in consumption. The nature of the fuel cell 1 used conditions in part the temperature at which water can be carried by heat Qs. FIG. 3 is a diagram showing schematically the evolution of different thermodynamic quantities of the system as a function of the temperature prevailing in the fuel cell at ambient pressure (1 atmosphere). Curve 9 corresponds to the heat that must be supplied to the endothermic reaction that occurs in the electrolysis fuel cell. This heat is equal to the product of the temperature T in the fuel cell 1 by the entropy difference AS between the entropy before the electrolysis and after the electrolysis in the fuel cell. A first phase represented by the band 101 of FIG. 3 comprises a linear increase of this heat with the temperature T. The sudden drop in the heat required at 100 ° C. is explained by the phase transition that the passing water undergoes. then from the liquid state to the vapor state. The second phase of evolution of the curve 9 is also a linear growth between 100 ° C. and 1000 ° C. It is interesting to note that the heat required increases with temperature T. Curve 8 represents the difference in free enthalpy AG or Gibbs energy 20 of the endothermic reaction. This energy is the minimum energy required in electrical form to produce oxygen and hydrogen by hydrolysis. Curve 7 represents the enthalpy difference ΔH of the endothermic reaction, which corresponds to the total energy to be supplied in order to be able to produce it, by supplying heat: Q = TAS and electricity: AG.
    [0029] As shown in FIG. 3, the total energy to be supplied to the endothermic reaction is greater when the water is in the liquid state than in the vapor state. This difference results in a drop in energy when the water undergoes a liquid / vapor phase transition as indicated by the interval 70 in FIG. 3. Therefore, the use of fuel cells 1 operating at temperatures above 100 ° C is preferred.
    [0030] It is interesting to note that in the vapor state, the total energy to be supplied to the endothermic reaction increases very little between 100 ° C and 1000 ° C. Because of this approximately fixed value of the total energy, and since the value of the heat Q to be supplied to the cell increases with the temperature, the value of the energy to be supplied in electrical form decreases with temperature. Therefore, in order to save the energy in electrical form spent on electrolysis, it may be advantageous to use fuel cells compatible with high operating temperatures, in particular between 650 ° C and 850 ° C. represented by the band 100 in FIG. 3. The interval represented by the arrow 80 in FIG. 3 corresponds to the thermal energy to be supplied to the cell at 800 ° C. in the electrolysis regime. This heat can be supplied by the water in the vapor state itself. The electrical energy to be supplied at 800 ° C. is represented in FIG. 3 by the gap 81. The solid oxide ceramic fuel cells 1 are the best candidates to meet this criterion. Depending on the constituent materials of these ceramic cells, the operating temperature in the electrolysis regime can be between 400 ° C. and 600 ° C. for the proton-conducting materials and between 650 ° C. and 850 ° C. for the materials. ion conductors such as in particular yttrie zirconia. The commercial cells for cogeneration are composed of two strontium-doped lanthanum cobalt type electrodes for the positive electrode and a cermet (ceramic and metal mixture) of nickel and yttriated zirconia for the negative electrode seat of the oxidation reaction in discharge and reduction regime electrolysis. The use of solid oxide ceramic cells also has the advantage that they allow the oxygen- and hydrogen-producing endothermic reaction efficiently to be carried out without the need for expensive noble metal catalysts such as platinum. For illustrative purposes only, an example will be given below of the quantities of energy involved in the system described above showing that the thermal and energy management of the system makes it possible to achieve overall energy efficiencies close to 80%.
    [0031] In this illustrative case, it is assumed that the energy source 5 provides 10 kWh of electrical energy to the fuel cell 1 in the electrolysis regime. 5% of this energy is lost by non-recoverable thermal losses, which represents about 0.5 kWh. It is assumed that in the electrolysis regime, the fuel cell 1 has a yield of 95% with respect to the lower calorific value and that the power supply of the cell generates an endothermic reaction according to the exothermic mode described above. . The adsorption of hydrogen in the material of the hydrogen storage and release device generates 2.9 kWh of energy in the form of heat. A portion corresponding to 1.9 kWh of this energy is used to vaporize water from source 6 to bring it to a temperature of 800 ° C. The remaining energy portion of 1.0 kWh is used for heating a building. The thermal losses in the fluid circuit carrying the heat from the material represents about 10% of the 2.9 kWh of energy released, about 0.3 kWh. Thus, when the fuel cell operates according to the second endothermic reaction, 1 kWh of heat is used to meet a consumption requirement, supplying the plant 4 with heat. When the fuel cell operates in the discharge regime, according to the first exothermic reaction, the losses Ep represent about 10% of the total energy contributed by the hydrogen in the reaction. The hydrogen supply is assimilated to an energy input of 11 kWh. The losses Ep then represent 1.1 kWh of energy lost. The exothermic reaction generates 5.1 kWh of heat and 4.8 kWh of electricity. A portion corresponding to 2.9 kWh of the 5.1 kWh of heat produced is used to release the hydrogen stored in the material of the hydrogen storage and release device. The remaining portion of heat corresponding to 2.2 kWh of energy is recovered by heating the installation 4. The energy balance of this reaction is therefore as follows: for 10 kWh of total energy supplied to the system by the source 5 outside energy, 4.8 kWh of electrical energy is produced: which corresponds to a total electrical efficiency of 48%. - for 10 kWh of total energy supplied to the system, 1.0 kWh + 2.2 kWh of energy in the form of heat is recovered by being transported to plant 4. This corresponds to a total thermal efficiency of 32 %. The 10 kWh of total energy supplied thus makes it possible to use 4.8kWh + 1.0 kWh + 5 2.2 kWh or 8 kWh of energy in electrical and thermal form. Thus, the total energy efficiency of the system is 80%. The invention is not limited exclusively to the embodiments presented above.
    [0032] By way of example, the hydrogen-based compound used may be methanol, methane, or any other hydrogen-based compound that may be involved in the exothermic reaction of a fuel cell, without the need for other changes in the arrangement of the system described above. The material for storing the hydrogen-based compound may also be in various forms. In addition to metal hydrides, any other material that makes it possible to adsorb a compound based on hydrogen could be envisaged, particularly other families of hydrides than that presented above. The adsorption of dihydrogen causes a release of heat at a given pressure. The reverse hydrogen release reaction requires external heat input at a given pressure. However, the liberation and storage of hydrogen may, in a complementary manner, be regulated by a modification of the pressure prevailing in the hydrogen storage and release device. By lowering the pressure, the heat required to release the stored hydrogen is reduced. A combination of the two parameters: pressure and heat, influencing storage reactions and hydrogen release allows adjustments to be made to further increase the overall efficiency of the system.
    权利要求:
    Claims (16)
    [0001]
    REVENDICATIONS1. A method of thermal management of a system for storing energy and co-generating electricity and heat, the system comprising: - a fuel cell (1) capable of producing electricity and heat according to a first recombination exothermic reaction of oxygen and a compound based on hydrogen and capable of producing the hydrogen-based compound according to a second endothermic reaction by decomposition of a fluid comprising hydrogen, - a device for storing and releasing hydrogen (2), comprising a material configured to generate heat upon storage of the hydrogen-based compound and releasing the hydrogen-based compound in the presence of heat, the method comprising: when the fuel cell operates in accordance with the second endothermic reaction: - convey the hydrogen-based compound released by the second endothermic reaction to the material that comprises the device of storing and releasing hydrogen, thereby generating heat (Qs); the method being characterized in that it further comprises, when the fuel cell operates according to the second endothermic reaction: - conveying at least a portion of the heat (Qs) from the material to a source (6) of the fluid comprising hydrogen, so that the fluid comprising hydrogen is brought to a predetermined temperature (Tc); and - supplying the fuel cell with fluid raised to the predetermined temperature (60) and electricity for decomposing the fluid to a predetermined temperature, thereby generating the hydrogen-based compound to be stored in the material of the storage and release of hydrogen.
    [0002]
    The thermal management method of claim 1, further comprising, when the fuel cell operates according to the first exothermic reaction: - conveying at least a portion of the heat produced by the first exothermic reaction from the fuel cell to the material, thereby releasing the hydrogen-based compound stored in the material; and - feeding the hydrogen-based compound from the material to the fuel cell for feeding the first exothermic reaction.
    [0003]
    The thermal management method according to any one of the preceding claims, further comprising, when the fuel cell is operating according to the first exothermic reaction: conveying at least a portion of the heat from the fuel cell to a cold source ; and when the fuel cell operates according to the second endothermic reaction: - convey at least a portion of the heat from the material to the cold source. 15
    [0004]
    The thermal management method of any of the preceding claims, further comprising: heating the fluid to a predetermined temperature of from 300 ° C to 1000 ° C. 20
    [0005]
    The thermal management method of claim 4, further comprising: - heating the fluid to a predetermined temperature of between 650 ° C and 850 ° C.
    [0006]
    The thermal management method of any one of the preceding claims, further comprising: supplying the fuel cell with electricity from a power source; and storing excess electricity from the energy source in the form of the hydrogen-based compound in the material of the hydrogen storage and delivery device by decomposing the fluid brought to the predetermined temperature in the fuel cell operating according to the second endothermic reaction.
    [0007]
    7. System for storing energy and for cogeneration of electricity and heat, comprising: a fuel cell (1) capable of producing electricity and heat according to a first exothermic reaction by recombination of oxygen and a a hydrogen-based compound capable of producing the hydrogen-based compound according to a second endothermic reaction by decomposition of a fluid comprising hydrogen by consuming electricity and heat; a hydrogen storage and release device (2) comprising a material configured to generate heat upon storage of the hydrogen-based compound, and releasing the hydrogen-based compound in the presence of heat; characterized in that the system further comprises a source (6) of said fluid comprising hydrogen, said source being connected to the fuel cell, - a first connection (22) connecting the source of said fluid to the storage device and releasing hydrogen, said first connection being for conveying heat generated during storage of the hydrogen-based compound in the material to the source of said fluid.
    [0008]
    The system of claim 7, wherein the fuel cell is connected to the hydrogen storage and delivery device by: a second connection (20) for conveying the hydrogen-based compound released from the material to the fuel cell; and - a third connection (10) for conveying the heat generated in the fuel cell to the material.
    [0009]
    9. System according to any one of claims 7 or 8, wherein the device 25 for storing and releasing hydrogen is configured to store the hydrogen-based compound at a pressure of less than 15 bar.
    [0010]
    The system of any one of claims 7 to 9, wherein the material comprised in the hydrogen storage and delivery device comprises a metal hydride.
    [0011]
    11. System according to claim 10, in which the metal hydride is chosen from compounds of the magnesium family such as MgH2, NaMgH2, Mg2FeH6, Mg2NiH4. 3033943 25
    [0012]
    The system of any one of claims 7 to 11, wherein the fuel cell comprises a solid oxide ceramic cell.
    [0013]
    The system of claim 12, wherein the solid oxide ceramic cell comprises a material selected from ionic conductive materials and protonic conductive materials.
    [0014]
    The system of claim 13, wherein the ionically conductive material is yttria and the proton conductive material is a barium, indium and titanium compound.
    [0015]
    15. System according to any one of claims 7 to 14, further comprising a power source (5) supplying the fuel cell. 15
    [0016]
    16. The system of claim 15 wherein the energy source is selected from: a connection to an electrical network and a photovoltaic panel.
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    同族专利:
    公开号 | 公开日
    WO2016146956A1|2016-09-22|
    EP3271962B1|2019-04-10|
    EP3271962A1|2018-01-24|
    FR3033943B1|2017-03-31|
    JP2018513915A|2018-05-31|
    CN107534171A|2018-01-02|
    WO2016146956A9|2017-01-12|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1552272A|FR3033943B1|2015-03-19|2015-03-19|METHOD OF THERMALLY MANAGING A SYSTEM FOR COGENERATION OF ELECTRICITY AND HEAT AND ASSOCIATED SYSTEM|FR1552272A| FR3033943B1|2015-03-19|2015-03-19|METHOD OF THERMALLY MANAGING A SYSTEM FOR COGENERATION OF ELECTRICITY AND HEAT AND ASSOCIATED SYSTEM|
    CN201680024468.1A| CN107534171A|2015-03-19|2016-03-18|Method and its related system to carrying out heat management for the system of cogeneration of heat and power|
    JP2017549307A| JP2018513915A|2015-03-19|2016-03-18|Method and associated system for thermally managing a system for combined power and heat|
    PCT/FR2016/050601| WO2016146956A1|2015-03-19|2016-03-18|Method for thermally managing a system for the cogeneration of electricity and heat and associated system|
    EP16712065.8A| EP3271962B1|2015-03-19|2016-03-18|Method for thermally managing a system for the cogeneration of electricity and heat and associated system|
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