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    • 专利摘要:
    Tank for storing hydrogen by absorption in a hydrogen storage material, comprising a shell (4) of longitudinal axis (X) closed at its two longitudinal ends, a hydrogen supply a hydrogen evacuation released and at least one heat transfer element (8) mounted transversely in the shell (4) and in contact with the inner surface of the ferrule (4), said heat transfer element having an outer peripheral edge formed of tongue in elastic contact with the inner surface of the shell (4) so that the contact between the heat transfer element (8) and the ferrule (4) is maintained during temperature changes during the hydrogen charging and discharging phases, said heat transfer element (8) being intended to provide heat transfers to and from the storage material to be contained in the tank.
    公开号:FR3014998A1
    申请号:FR1362782
    申请日:2013-12-17
    公开日:2015-06-19
    发明作者:Olivier Gillia；Albin Chaise；David Vempaire；Laurent Peyreaud
    申请人:Commissariat a lEnergie Atomique CEA；McPhy Energy；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD AND PRIOR ART The present invention relates to a hydrogen storage tank with metal hydrides and to a hydrogen storage device comprising at least one such reservoir. . We are looking for alternative energies for oil because, in particular, the reduction of oil reserves. One of the promising vectors for these energy sources is hydrogen, which can be used in fuel cells to produce electricity. Hydrogen is a widespread element in the universe and on Earth, it can be produced from natural gas or other hydrocarbons, but also by simple electrolysis of water using for example the electricity produced by solar or wind energy.
    [0002] Hydrogen batteries are already used in some applications, for example in motor vehicles but are still not widespread, especially because of the precautions to be taken and difficulties in storing hydrogen. Hydrogen can be stored in compressed form between 350 and 700 bar, which poses safety and energy consumption problems for gas compression. It is then necessary to provide tanks able to hold these pressures, knowing furthermore that these tanks, when mounted in vehicles, may be subjected to shocks. It can be stored in liquid form, however this storage ensures a low storage efficiency and does not allow storage over long periods.
    [0003] The passage of a volume of hydrogen from the liquid state to the gaseous state under normal conditions of pressure and temperature produces an increase in its volume by a factor of about 800. Hydrogen reservoirs in the form of liquid are generally not very resistant to mechanical shock, this poses significant safety problems. There is also the storage of hydrogen called "solid" in the form of hydride. This storage allows significant storage compactness and implements a moderate hydrogen pressure while minimizing the energy impact of storage on the overall efficiency of the hydrogen chain, i.e. from its production to its conversion to another energy. The principle of solid storage of hydrogen in the form of hydride is as follows: some materials and in particular some metals have the ability to absorb hydrogen to form a hydride, this reaction is called absorption. The hydride formed can again give hydrogen gas and a metal. This reaction is called desorption. Absorption or desorption occurs as a function of hydrogen partial pressure and temperature.
    [0004] Absorption and desorption of hydrogen on a powder or a metal matrix M is done according to the following reaction: Storage: heat released (exothermic) M ,,., __, '- + x, 1 u 12 .41: RiFi x + AH (Heat) Destocking: Heat to be supplied (endothermic) - M being the metal powder or matrix, - MHx being the metal hydride.
    [0005] For example, a metal powder is used which is brought into contact with hydrogen, an absorption phenomenon appears and a metal hydride is formed. The hydrogen is liberated according to a desorption mechanism. Hydrogen storage is an exothermic reaction, i.e., which releases heat, while hydrogen release is an endothermic reaction, i.e., which absorbs heat.
    [0006] In addition, the material absorbing hydrogen increases in volume. When the material absorbs hydrogen, there is heat release, the equilibrium pressure, that is to say the pressure beyond which the material is loaded with hydrogen, increases, it quickly reaches the level of the hydrogen supply pressure, which has the effect of blocking the hydriding reaction. In order to fight against this phenomenon which is harmful to a rapid loading of the tank, it is necessary to cool the material. Conversely, in the direction of hydrogen liberation, a heat supply must take place in order to increase the equilibrium pressure and to have a source of pressure above the pressure that is wish to have a tank outlet. Means are then provided to ensure exchanges of heat between the material inside the tank and a cold source or a hot source depending on whether it is a charging or discharging phase. US 4,667,815 discloses a metal hydride storage device having a cylindrical vessel in which hydride-containing cans are superposed. Each box has an upper portion provided with an outer flange surrounding a recessed portion of a lower bead, the flange being in contact with the interior surface of the vessel, thereby providing heat exchange between the interior and the interior of the vessel. outside.
    [0007] In order to ensure a good conduction of heat through the tank, it is desirable to ensure good contact between the boxes and the tank. Now, on the one hand because of the differential expansions between the material of the ferrule and the material of the boxes, and on the other hand geometrical defects, the good thermal contact between the ferrule and the boxes can not be ensured. SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a hydrogen storage device in which heat exchange is improved. The previously stated purpose is achieved by a storage device having a vessel of longitudinal axis for receiving the storage material and heat transfer elements mounted in the vessel and in contact with the interior of the vessel. The storage material is disposed in the vessel so as to exchange heat with the heat transfer elements. The elements comprise an outer peripheral edge in elastic support against the inner face of the vessel so that contact between the heat transfer elements and the vessel is ensured despite differential expansion and / or geometric defects, and heat transfer between the conductive elements and the ferrule are maintained. Due to the elasticity of the peripheral edge, it compensates for the geometric variations between the tank and the heat transfer elements, which ensures a maintenance of thermal transfers throughout charging and discharging cycles. Advantageously, the heat transfer element or elements comprises a central zone and the peripheral edge comprises a plurality of tongues folded with respect to this central zone, the tongues ensuring contact with the wall of the vessel and deforming about their axis. folding. Advantageously, the central zone and the tongues are in one piece. Very advantageously, the central zone may comprise radial cuts, which provides greater flexibility to the heat transfer element and allows the heat transfer element a greater amplitude of deformation. The subject of the invention is therefore a reservoir intended for the storage of hydrogen by absorption in a hydrogen storage material, comprising a ferrule of longitudinal axis closed at its two longitudinal ends, a hydrogen supply and an evacuation of hydrogen. the hydrogen released and at least one heat transfer element mounted transversely in the ferrule and in contact with the inner surface of the shell, said heat transfer element having an outer peripheral edge in elastic contact with the inner surface of the ferrule so that the contact between the heat transfer element and the ferrule is maintained during temperature variations during the phases of charging and discharging hydrogen, said heat transfer element being intended to ensure heat transfer to and from the material storage intended to be contained in the tank. In an advantageous example, the heat transfer element comprises a substantially flat central zone and the peripheral edge comprises tongues surrounding the central zone, said tongues forming an angle with the central zone. Preferably, the tongues are formed integrally with the central zone and are folded with respect to the central zone.
    [0008] For example, the ferrule has a substantially circular section and the heat transfer element has a substantially circular shape, a dimension between a base of the tongues connected to the central zone and a free end of the tongues being between 0.5% and 75% of the inner radius of the ferrule. The heat transfer element may comprise at least one through hole The heat transfer element may comprise a plurality of through holes having means capable of allowing the hydrogen to pass and preventing the passage of the storage material in the form of powder. The reservoir may comprise at least one duct extending along the longitudinal axis in the shell and passing through the heat transfer element through said through hole. The through hole of the heat transfer element may advantageously be flanked by tongues in elastic contact with the conduit. The through hole is advantageously located in the center of the central zone and in which the heat transfer element has radial cutouts extending from the through hole. The reservoir advantageously comprises means capable of passing the hydrogen and preventing the passage of the storage material in the form of powder disposed at least between the tabs of the peripheral edge and / or the tongues of the through hole.
    [0009] In an exemplary embodiment, the heat transfer element may comprise radial cuts extending from the peripheral edge and not opening into the central hole. In an advantageous example, the reservoir comprises at least one container disposed on the heat transfer element, said container being intended to contain hydrogen storage material. A clearance can be provided between the container and the inner surface of the shell. In an exemplary embodiment, the bottom of the container is formed by the heat transfer element.
    [0010] The reservoir may advantageously comprise a thermal conductive structure inserted in the container. The reservoir may comprise a plurality of heat transfer elements defining, in pairs, a compartment intended to contain thermal storage material.
    [0011] Preferably, the container is disposed in contact between two heat transfer elements. A thermal management system in contact with the outside of the ferrule may advantageously be provided. The reservoir may comprise a storage material in the form of a powder, the heat transfer elements being embedded in the powder or a powdered storage material contained in at least one container or a pelletized storage material placed in contact with each other. between two heat transfer elements, hydrogen diffusion elements may be provided in contact with the pellets. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will be better understood from the following description and attached drawings in which: FIGS. 1A, 1B and 1C are, respectively, plan views, side views and in perspective of a heat transfer element according to the invention, - Figure 1D is a longitudinal sectional view of a portion of the element of Figure 1A, - Figures 2A to 2E are schematic representations of examples of mounting device using heat transfer elements of FIGS. 1A to 1C, - FIGS. 3A and 3B are views from above and in perspective respectively of another embodiment of a heat transfer element according to the invention, FIG. 3C is a sectional view of the element of FIGS. 3A and 3B along the plane AA in a first state of deformation and in a second state of deformation; FIGS. 4A to 4C are different views of another example of realizing a storage device using heat transfer elements according to the invention.
    [0012] DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS In the remainder of the description, the metal hydrides will be referred to as "storage material". The term "hydriding cycle" refers to an absorption phase followed by a hydrogen desorption phase.
    [0013] In the following description, the tank or tanks described have a cylindrical shape of revolution, which represents the preferred embodiment. Nevertheless any tank formed by hollow element having a longitudinal dimension greater than its transverse dimension, and having any section, for example polygonal or ellipsoidal is not beyond the scope of the present invention. A hydrogen storage device according to the invention comprises one or more tanks containing storage material and a thermal management system for supplying and extracting heat to release hydrogen and store it respectively in the storage material. .
    [0014] Figures 2A to 2C show schematic representations of storage material tanks. The tank 2 comprises a ferrule 4 of longitudinal axis X closed at a lower end by a lower bottom 6. The tank also comprises an upper bottom (not shown) closing the upper end of the shell 4. The shell 4 is, in the example shown, of circular section. The reservoir is intended to be generally oriented so that the longitudinal axis X is substantially aligned with the direction of the gravity vector. However during its use, especially in the case of embedded use, its orientation may change. The reservoir comprises means (not shown) for supplying hydrogen and collecting hydrogen. The reservoir also comprises heat transfer elements 8 mounted inside the ferrule 4. An exemplary embodiment of one of these heat transfer elements is shown in FIGS. 1A to 1C. These means provide thermal conduction oriented transversely between the storage material M and the ferrule. The heat transfer element 8 has substantially the shape of a flat-bottom circular cup having a central zone 10 and on its radially outer periphery tabs or lugs 12 which are inclined with respect to the plane of the central zone 10. The tongues 12 are advantageously made in one piece with the central zone 10, by cutting and folding. The tongues may be substantially planar or may have a curvature, in the latter case, the contact between the tongues and the ferrule is tangentially, it is then increased relative to flat tabs for which the contact with the ferrule is linear. . In the example shown in Figure 1D, the tabs form with the central zone 10 an angle greater than or equal to 90 °. When mounting the heat transfer element in the shell, the tongues 12 are radially deformed radially inwardly. A small plastic deformation can occur, but the contact will always be assured by the elastic return part of the tongues. The heat transfer elements 8 are made of a material offering good thermal conductivity with respect to the storage material, and preferably a very good thermal conductivity such as copper or aluminum. Preferably, the material of the heat transfer element has a thermal conductivity at least ten times greater than that of the storage material. For example, the distance between the end of the tabs 12 attached to the central zone 10 and their free end is between a few percent to a few tens of percent of the inner diameter of the shell, for example between 0.5% and 75%, the inner diameter of the ferrule, for example equal to 10%. Thus they have a sufficient surface in contact with the inner surface of the shell 4 to conduct the heat. The dimensions of the heat transfer elements 8 are chosen so as to allow their mounting in the ferrule and to ensure elastic deformation of the tongues. Preferably, to have a good thermal contact between the elements 8 and the ferrule, the diameter at the periphery of the tongues is slightly greater than that of the inner diameter of the ferrule. For example, the thermal transfer elements at the periphery of the tongues may have a diameter 1 to 2 mm greater than the inside diameter of the ferrule. This value may depend on the geometric defect measured on the ferrule. Preferably, the value of the diameter Oi at the periphery of the tongues is determined by placing itself at the elastic limit of the material of the heat transfer elements 8 when it is equal, after assembly, to the average diameter of the ferrule. In order to ensure contact with all the tongues, this diameter value Oi is increased by the difference between this diameter and the largest diameter of the ferrule, the ferrule not being perfectly circular: ## EQU1 ## max. It may be possible to choose a diameter Oi more importantly, in this case the tabs will deform more plastically.
    [0015] When mounting the heat transfer elements 8 in the shell 4, the tongues 12 deform primarily elastically but plastic deformation can also take place. The residual elasticity ensures a permanent contact between each tongue and the inner wall of the ferrule.
    [0016] The thickness of the heat transfer elements is chosen according to the intended application, the kinetics of loading or unloading of the hydrogen may be different. The thickness of the heat transfer element is chosen as a function of the heat flux to be removed by conduction. For example, the heat transfer elements may have a thickness of the order of 1 mm.
    [0017] FIG. 2A schematically shows heat transfer elements 8 mounted in the shell 4. The heat transfer elements 8 are held in the shell 4 by the radial elastic deformation of the tongues 12. The heat transfer elements delimit compartments for the storage material. The contact stresses between the heat transfer elements and the ferrule may be sufficient for the heat transfer elements to support the storage material. Alternatively, as will be described in more detail below, the support of the material is provided by superimposed buckets 20, the elements 8 being interposed between the buckets (Figures 2A and 4B). In a variant, each stage rests on the powder of the lower stage (FIG. 2C). This material can be in different forms. It can be in the form of pellets formed of a hydride compacted with other materials to ensure the cohesion of the pellets and improve the conduction of heat, for example the hydride can be mixed with carbon. These pellets retain their shape substantially during the hydriding cycles (FIG. 2C). The storage material may be in the form of loose powder, the storage device is then filled directly with the powder (Figure 2A or 2B). The storage material may be in the form of slabs or massive ingots or more generally of polyhedral pieces of millimeter or centimeter size. The material in these different forms simplifies filling. During the hydriding cycles, the material tends to swell as it absorbs hydrogen. The heterogeneous swelling by nature of the material causes fragmentation, the man of the art also said decrepitation, of it powder. This case may correspond to the examples of FIGS. 2A and 2B. In the example of FIGS. 1A to 1C, the heat transfer element comprises holes 14 distributed in the central zone 10 allowing the passage of hydrogen from one compartment to the other during the charging and discharging phases. These holes 14 may be of identical or variable section. In the case where the storage material is in the form of powder or slab intended to decrepitate, the holes 14 are closed by means ensuring the passage of hydrogen but preventing the passage of the powder. These means are for example formed by a fine grid, a metal fabric, a porous sintered material or even a filter made of organic or polymeric material, under the sole constraint of not polluting the hydrogen storage material or hydrogen. even under the conditions of temperature and pressure of use of the hydride material. In the example shown, the holes are of different sections, the radially outermost holes being of larger section. The holes could be of constant section. The total section of the holes is determined according to the flow of hydrogen that must be passed through.
    [0018] For example, the means preventing the passage of the powder through the holes are chosen so as to prevent the passage of fine particles of hydride, between 1 and 5 um in the case of a LaNi5-type hydride, for example. The passage of hydrogen may also take place at the periphery of the heat transfer elements 8, between the tongues, in particular in the embodiments of the figures of FIGS. 2A and 2C. In the example shown, the central zone of the heat transfer element comprises a central passage 16 which is also bordered by tongues 18 oriented towards the axis of the heat transfer element. This central passage 16 is for example intended for the passage of a conduit (not shown) for the flow of a coolant providing or removing heat depending on the step of the hydriding cycle. The tongues 18 are elastically deformed by the tube, good contact is then obtained also ensuring good heat transfer between the conduit and the heat transfer elements. In addition, the tongues 18 in elastic contact with the conduit allow at least partially closing the clearance between the conduit and the edge of the through hole and thus prevent at least partly the fall of powder in the lower compartment. Advantageously, a filter element as described above can be envisaged to prevent the hydride material in powder form from passing into the interstices between the tongues 12 or 18 without preventing the passage of hydrogen. For example, it is possible to place a fine filtering grid over the tongues supporting the hydride material. This through hole 16 may serve alternately to the passage of a supply conduit and hydrogen collection. The conduit is for example made of porous material, for example made of Poral® or pierced with through holes, and connected to a supply circuit and hydrogen collection; the size of the holes in the tube is small enough to prevent the passage of the powder. For example, it is possible to use a duct made of porous material calibrated to a size of 1 μm to ensure a hydride powder seal and a passage of hydrogen. In this case, the tabs 18 are not required because it does not seek heat exchange between the heat transfer elements and the supply duct and collection of hydrogen. Nevertheless, as indicated above, the tongues 18 in elastic contact with the duct can make it possible to close at least partially the clearance between the duct and the edge of the through hole and thus prevent at least part of the falling of powder in the compartment inferior.
    [0019] Several passage holes for the passage of several ducts may be provided, it is possible to envisage one or more circulation ducts of a coolant and / or one or more conduits for supplying and collecting hydrogen. We will now describe various examples of reservoir comprising the heat transfer elements according to the invention.
    [0020] In FIG. 2A, the storage material M in powder form in each compartment is received in a container resting on a heat transfer element. The container is such that its side wall is not in contact with the shell, providing a lateral clearance between the shell and the container, thus avoiding a force applied to the shell when the storage material swells. This side game also allows the passage of hydrogen. This container 20 ensures the retention of the powder and prevents it from being in contact with the wall of the ferrule and further ensures by contact with the heat transfer element thermal conduction. The containers are stacked, the lower containers supporting the upper containers. The containers are for example stainless steel, copper, aluminum. Alternatively, it can be envisaged that the side wall of the container is made of plastic material and that the bottom of the container is formed directly by the element 8. The powder storage material M is then in direct contact with the element 8 which ensures good heat transfer between the material and the element while using a plastic material to partially ensure the retention of the powder. Advantageously, the container 20 of a compartment is in contact by its upper end with the heat transfer element 8 of the upper compartment 20. The heat transfer element 8 of the upper compartment forms a lid limiting the leakage of the powder by the top of the container and further this contact also allows a heat exchange. Thus, in this advantageous embodiment, heat exchange takes place both at the bottom of the container and at the top of the container. In FIG. 2B, the storage material in powder form is in direct contact with the ferrule. In this embodiment, the height of the powder bed is chosen to be smaller than the diameter of the powder bed in order to neglect the mechanical pressure exerted by the powder on the ferrule relative to that of hydrogen. In this embodiment, stages are made in the tank by mounting transverse plates 22 and heat transfer elements 8 according to the invention are arranged in the powder thickness. In the example shown, the heat transfer elements 8 are embedded in the powder, each heat transfer element then thermally exchanges with the powder by its lower face and its upper face. In this example, each heat transfer element undergoes mechanical pressure from the powder on both sides. The elements 8 can slide along the axis of the ferrule during swelling of the material when it is loaded. The elements can slide in the ferrule at each loading / unloading phase or can reach a substantially fixed position depending on the stresses between the elements and the ferrule. Advantageously, a means ensuring the retention of the powder and the passage of hydrogen may be provided to prevent the powder from passing through the elements 8 either at the holes 14 or at the interstices between the tongues 12 and smallpox and between the tabs 18 and the duct. In FIG. 2C, the storage material M is in the form of a tablet. Each pellet is disposed on a heat transfer element. In the example shown and advantageously, each tablet is in contact by its lower face and its upper face with a heat transfer element increasing the heat exchange and ensuring homogeneous heat exchange in each pellet. In this example, plates of porous material are disposed in the porous material perpendicular to the longitudinal axis, improving the diffusion of hydrogen. Indeed, the pellets are dense with little porosity. The porous plates provide distribution of hydrogen all over the wafer to minimize the diffusion length of hydrogen in the wafer. FIG. 2D shows a preferred embodiment of the invention in which the heat transfer elements 8 also form support elements for the powder storage material M. Elements are arranged at the zones between the tongues and possibly at the holes 14 and the passage 16 if they are provided, so as to let the hydrogen and retain the powdered storage material, avoiding an accumulation thereof in the tank bottom. A free volume V is provided between the top of the powder and the bottom of the upper heat transfer element in order to allow free swelling of the storage material in the charging phase and to prevent interaction between the powder and the element. superior heat exchange. In this example, the elements 8 are held in place in the ferrule by friction.
    [0021] In Figure 2E, we can see a variant of the reservoir of Figure 2D, wherein spacers 17 are advantageously provided between the heat transfer elements 8 to ensure good positioning with respect to each other over time. Indeed, for example following a shock or a fall of the tank, it could be that one or more elements 8 slide upwards along the shell. The spacers are for example formed by columns, for example fixed to the bottom of the elements 8. Alternatively, the columns may be carried by a single crown as shown schematically in Figure 2E. Thanks to these spacers, the space between the elements is maintained. The use of these spacers is particularly advantageous in the case of tank with a large number of stages. FIGS. 4A to 4C show an example of a practical embodiment of a storage tank according to the invention, comprising a plurality of heat transfer elements 8 each delimiting a stage. Each stage comprises a container 20 resting on a heat transfer element 8. The container is such that the hydride forms a thin bed, i.e. offering a low slenderness. Moreover, the containers are such that they are not in mechanical contact with the ferrule. In the example shown and advantageously, each container 20 has a container structure 28 delimiting in the container sub-compartments improving the heat transfer in the thickness of the hydride bed, and preventing the hydride bed n has lateral flow in the event that the tank is tilted during handling. In the example shown, the sub-compartments are of square or rectangular shape but could be provided that they are for example honeycomb. Advantageously and as shown in Figures 4B and 4C, notches 29 are formed in the free edges of the bins to facilitate the passage of hydrogen. These notches are not shown in Figure 4A for clarity. In addition, the reservoir comprises a thermal management system comprising a pipe 30 wound on the outer surface of the shell 4 and wherein is intended to circulate a coolant providing or removing heat depending on the phase of the cycle. According to an advantageous variant, it is intended to bathe the ferrule 4 in a heat-transfer liquid bath. It can be very advantageously provided that the bottom of the container is formed directly by the heat transfer element further improving the transfers between the powder and the heat transfer element. By way of example, the reservoir may have the following characteristics: the heat transfer elements are made of copper and have a thickness of 2 mm; the heat transfer elements have a height of 10 mm, the ferrule with a diameter of 300 mm, the hydride bed has a thickness of 20 mm, the inserted structure has a pitch greater than 20 mm. An exemplary embodiment of the heat transfer elements will now be described. In a first step, the heat transfer elements are made by cutting in a sheet of eg copper or aluminum. In a next step, the tabs are cut. Alternatively, this step can be performed simultaneously with the first step. In addition material may be removed to avoid overlapping of the tabs when folded. In a next step, the tabs 12 are folded so that they are slightly inclined outwards and define an outer radius greater than that of the central portion 10. If the heat transfer elements comprise holes, these These are made for example by means of a punch, several in the case where the holes are of different section. The holes are preferably made before folding the tongues. In the case where the through hole 16 is flanked by tabs 18, they can be made in the manner described for the tabs 12. The material withdrawal is not used for the tabs 18. The embodiment of the transfer elements thermal is very simple and low cost. The realization of the tank is the following. A first heat transfer element 8 is inserted into force in the shell 4, the tabs 12 upwards. The tabs 12 fold radially inward mainly elastically. The heat transfer element 8 is moved longitudinally in the ferrule until it reaches the desired position. Due to the residual elasticity, the heat transfer element 8 is held in position in the shell 4 and the tabs 12 are in contact with the inner surface of the shell 4. The storage material M is then put in place, in the form of powder, cake or lozenge. Depending on the form in which the material is presented, a container 20 may be provided to contain the powder. In a variant, the internal structure of the reservoir comprising the material M is produced and the assembly is then introduced into the shell. A second heat transfer element 8 is forcefully introduced into the ferrule 4 and is displaced until it reaches the desired position, for example in contact with the chip previously put in place. The above steps are repeated as many times as necessary. The tank is then closed and the connections to the supply and collection circuit of the hydrogen and the thermal management system are realized. In the case where one or more conduits extend longitudinally in the shell, they are put in place before the introduction of the heat transfer elements. The heat transfer elements have passage holes. The heat transfer elements, when mounted in the ferrule, are traversed by the conduits. We will now explain the operation of the heat transfer elements.
    [0022] As shown in FIGS. 4A and 4C, the thermal management system may for example be formed by a tube wound around the tank, in which a coolant circulates, this coolant ensures by heat exchange with the shell the extraction of heat or the heat input. Alternatively, the thermal management system is formed by a coolant bath in which is disposed the reservoir, or a jacket that surrounds the reservoir. In a hydrogenation phase, i.e. of hydrogen charge, hydrogen feeds the reservoir. The hydrogen is either fed through a porous conduit which passes through the different compartments, or circulates between the ferrule 4 and the heat transfer elements 8 between the tongues 12 and / or through the holes 14 made in the heat transfer elements 8. Absorption of hydrogen by the storage material causes heat generation. This heat must be evacuated so as not to slow down or stop the hydriding. Due to the presence of the heat transfer elements 8 via the tabs 12 and their permanent contact with the shell 4, the heat is discharged to the outside through the heat transfer elements 8. The heat can also pass radially without passing through the heat transfer elements, if for example the material height M is large in front of the material diameter M. Even if the expansion coefficient of the heat transfer elements 8 is greater than that of the shell 4, this differential is absorbed by the elastic deformation of the tongues 12 at the periphery. Since the deformation comprises an elastic portion, the contact can be maintained durably during operation in absorption / desorption cycling of the hydrogen reservoir.
    [0023] In the dehydrogenation or discharge phase, the reaction of hydrogen requires a heat input. The heat is then supplied by the heat transfer elements 8 in contact with the shell 4 which itself is heated by the coolant. The present invention also offers the advantage of adapting to defects in circularity and diameter of the ferrule. Indeed, the tubes made in boilermaking, and for which the cost remains economically interesting, are generally not very geometric precision. The elastic deformation provided by the tongues makes it possible to maintain thermal contact for a certain lack of circularity and diameter of the ferrule.
    [0024] It will be understood that the characteristics of the tank may vary according to the applications according to the specifications of the application, in particular with regard to the loading and unloading speeds of the tank. FIGS. 3A to 3C show another embodiment of a heat transfer element 108 comprising a central orifice 23 and first radial cutouts 24 extending from the central orifice over part of the radius of the zone. central 110 and second radial cutouts 26 extending from the radially outer edge to the central orifice 23 and extending over a portion of the radius. Preferably the cuts extend substantially radially. Preferably, the first and second cutouts 24, 26 are angularly distributed uniformly around the central orifice. The second radial cuts are made between the tabs. In addition, it is expected that a second radial cut is disposed between two first radial cuts. An element having only cutouts 24 or cutouts 26 is not outside the scope of the present invention. For example, the angle between two cuts 24 or two cuts 26 is between 5 ° and 70 °. In the example shown, the cuts are rectilinear. They may have another form.
    [0025] In the example shown, the central hole has a polygonal shape. Alternatively the hole could be round. Alternatively, tabs on the contour of the central hole may be provided. These are then oriented in the opposite direction to the outer fins, downwards in the example shown, so that the inner and outer tabs deviate at the same time. The heat transfer element thus produced has greater flexibility. It is then possible to vary the outer diameter of the heat transfer element while benefiting from an increased elastic deformation range.
    [0026] The amplitude of this variation is substantially greater than that which can be obtained with the heat transfer element of FIGS. 1A to 1C. An advantageous method of mounting this type of heat transfer element is to install them using their increased elasticity to fill the mounting clearance between the fins and the ferrule. The standard assembly thus forces the type elements 108 to adopt a conical configuration, as shown in the upper part of Figure 3C. The amplitude of elastic deformation is then increased relative to elements of type 8. This amplitude is materialized by the large diameter difference between the configuration of the element 108 (FIG 3C in the upper part), and the configuration at rest in flattened form (Fig. 3C in lower part). When mounting the stack, the element 108 is flattened between two pellets, this causes the increase in the outer diameter of the element 108 which causes the contact of the tongues with the wall of the ferrule. The contact thus benefits from a larger reserve of elastic deformation than the case of the elements 8. This type of installation makes it possible to have only a slight contact with the assembly (when inserted into the shell), the assembly is then facilitated because there is less friction tabs on the walls. This heat transfer element thus makes it possible to adapt to variations in the diameter of the ferrule. It will be understood that the representation of the ferrule is schematic and only by way of illustration.
    [0027] By way of example, heat transfer elements of FIGS. 3A to 3C made of aluminum with a thickness of 2 mm and an outside diameter of 300 mm can be adapted to a ferrule with an internal diameter of between 299 mm and 301 mm. This exemplary embodiment has the advantage of being able to adapt to geometrical defects by having a larger reserve of elastic deformation. The cuts in fact introduce a greater circumferential elastic deformability. As for the holes, provision can be made in the cutouts, preferably above the holes means to prevent the beam from falling into the lower compartment, for example this means is a grid, tissue, poral. These cuts can also be used for the passage of hydrogen, the distribution of the cuts advantageously provide a distribution and a uniform collection of hydrogen. The central hole can be used for the passage of a coolant pipe or for supply / collection of hydrogen. The device according to the present invention can be used to transport hydrogen, for on-board hydrogen storage for fuel cells or heat engine, for the stationary storage of hydrogen. The device can therefore be used as an onboard tank for means of transport, such as boats, submarines, cars, buses, trucks, construction equipment, two wheels, for example to supply a fuel cell or a heat engine. In addition, it can be used in the field of energy transportable power supplies such as batteries for portable electronic devices such as mobile phones, laptops, ....
    [0028] The device according to the present invention can also be used as a stationary storage system of energy in larger quantities, such as generators, for storing hydrogen produced in large quantities by electrolysis with electricity from wind turbines. , photovoltaic panels, geothermal, ....
    [0029] It is also possible to store any other source of hydrogen from, for example, reforming hydrocarbons or other processes for obtaining hydrogen (photo-catalysis, biological, geological, etc.).
    权利要求:
    Claims (22)
    [0001]
    REVENDICATIONS1. A tank for storing hydrogen by absorption in a hydrogen storage material, comprising a ferrule (4) with a longitudinal axis (X) closed at its two longitudinal ends, a hydrogen supply and an evacuation of the hydrogen released hydrogen and at least one heat transfer element (8) mounted transversely in the shell (4) and in contact with the inner surface of the shell (4), said heat transfer element having an outer peripheral edge in elastic contact with the inner surface of the shell (4) so that the contact between the heat transfer element (8) and the ferrule (4) is maintained during temperature changes during the hydrogen charging and discharging phases, said element heat transfer device (8) for providing heat transfers to and from the storage material to be contained in the tank.
    [0002]
    2. Tank according to claim 1, wherein the heat transfer element (8) comprises a substantially planar central zone (10) and the peripheral edge comprises tongues (12) surrounding the central zone (10), said tongues (12). ) forming an angle with the central zone (10).
    [0003]
    3. Tank according to claim 2, wherein the tongues (12) are formed integrally with the central zone (10) and are folded relative to the central zone (10).
    [0004]
    4. Tank according to claim 2 or 3, wherein the ferrule (4) is of substantially circular section and the heat transfer element (8) has a substantially circular shape, a dimension between a base of the tongues (12) connected at the central zone (10) and a free end of the tongues (12) being between 0.5% and 75% of the inside radius of the ferrule (4).
    [0005]
    5. Tank according to claim 1 or 2, wherein the heat transfer element (8) has at least one through hole (14, 16, 23).
    [0006]
    6. Tank according to claim 5, wherein the heat transfer element (8) has a plurality of through holes (14) having means adapted to pass the hydrogen and preventing the passage of the storage material in powder form. .
    [0007]
    7. Tank according to claim 5 or 6, comprising at least one duct extending along the longitudinal axis in the ferrule and passing through the heat transfer element (8) through said through hole (16).
    [0008]
    8. Tank according to claim 7, wherein the through hole (16) of the heat transfer element (8) is flanked with tabs (18) in elastic contact with the conduit.
    [0009]
    9. Tank according to one of claims 5 to 8, wherein the through hole (23) is located in the center of the central zone and wherein the heat transfer element comprises radial cuts (24) from the through hole ( 23).
    [0010]
    10. Tank according to one of claims 1 to 9 in combination with claim 2, comprising means adapted to pass the hydrogen and preventing the passage of powdered storage material disposed at least between the tabs of the peripheral edge. and / or the tongues of the through hole.
    [0011]
    11. Tank according to one of claims 5 to 10, wherein the heat transfer element comprises radial cuts (26) extending from the peripheral edge and not opening into the central hole (23). 25
    [0012]
    12. Tank according to one of claims 1 to 11, wherein the heat transfer element defines a compartment, said heat transfer element supporting the thermal storage material.
    [0013]
    13. Tank according to claim 12, comprising at least one container (20) disposed on the heat transfer element (8), said container (8) being intended to contain thermal storage material.
    [0014]
    14. The tank of claim 13, wherein a clearance is provided between the container (20) and the inner surface of the ferrule (4).
    [0015]
    15. Tank according to claim 13 or 14, wherein the bottom of the container (20) is formed by the heat transfer element (8).
    [0016]
    16. Tank according to claim 13 to 15, comprising a thermal conductive structure (28) inserted into the container (20).
    [0017]
    17. Tank according to one of claims 12 to 16, comprising a plurality of heat transfer elements (8), defining in pairs a compartment for containing hydrogen storage material.
    [0018]
    The tank of claim 17, wherein the container (20) is disposed in contact between two heat transfer elements (8).
    [0019]
    19. Tank according to one of claims 1 to 18, comprising a thermal management system in contact with the outside of the shell (4).
    [0020]
    20. Tank according to one of claims 1 to 19 comprising a storage material in powder form, the heat transfer elements (8) being embedded in the powder.
    [0021]
    21. Tank according to one of claims 13 to 16 and 18, comprising a powdered storage material contained in at least one container (20).
    [0022]
    22. Tank according to one of claims 1 to 19, comprising a pelletized storage material disposed in contact between two heat transfer elements (8), hydrogen diffusion elements may be provided in contact with the pastilles.10
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    同族专利:
    公开号 | 公开日
    EP3084287A1|2016-10-26|
    CA2934404A1|2015-06-25|
    FR3014998B1|2016-01-22|
    US20160327209A1|2016-11-10|
    WO2015091550A1|2015-06-25|
    JP2017503135A|2017-01-26|
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    US6626323B2|2002-02-21|2003-09-30|Energy Conversion Devices, Inc.|Vane heat transfer structure|
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    CN106764400A|2016-12-20|2017-05-31|大连爱特流体控制有限公司|A kind of metallic compound hydrogen-storing device|
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    法律状态:
    2015-12-31| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-29| PLFP| Fee payment|Year of fee payment: 4 |
    2018-01-02| PLFP| Fee payment|Year of fee payment: 5 |
    2019-12-31| PLFP| Fee payment|Year of fee payment: 7 |
    2020-12-28| PLFP| Fee payment|Year of fee payment: 8 |
    2021-01-15| TP| Transmission of property|Owner name: COMMISSARIAT A L'ENERGIE ATOMIQUE ET AUX ENERG, FR Effective date: 20201207 |
    2021-12-31| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362782A|FR3014998B1|2013-12-17|2013-12-17|HYDROGEN STORAGE TANK WITH IMPROVED THERMAL METAL HYDRIDES|FR1362782A| FR3014998B1|2013-12-17|2013-12-17|HYDROGEN STORAGE TANK WITH IMPROVED THERMAL METAL HYDRIDES|
    US15/105,399| US20160327209A1|2013-12-17|2014-12-16|Hydrogen storage tank comprising metal hydrides with heat exchanges|
    PCT/EP2014/078064| WO2015091550A1|2013-12-17|2014-12-16|Hydrogen storage tank comprising metal hydrides with heat exchanges|
    CA2934404A| CA2934404A1|2013-12-17|2014-12-16|Hydrogen storage tank comprising metal hydrides with heat exchanges|
    EP14812543.8A| EP3084287A1|2013-12-17|2014-12-16|Hydrogen storage tank comprising metal hydrides with heat exchanges|
    JP2016559681A| JP2017503135A|2013-12-17|2014-12-16|Hydrogen storage tank containing metal hydride for heat exchange|
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