Metal hydride hydrogen storage arrangement for use in a fuel cell utility vehicle and method of manufacturing the same
11611092 · 2023-03-21
Assignee
Inventors
- Mykhaylo Volodymyrovich Lototskyy (Durbanville, ZA)
- Yevgeniy Klochko (Goodwood, ZA)
- Ivan Tolj (Kastel Stari, HR)
- Moegamat Wafeeq Davids (Goodwood, ZA)
- Adrian J. Parsons (Three Anchor Bay, ZA)
Cpc classification
F17C2205/0142
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F17C11/005
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Y02P70/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M8/065
ELECTRICITY
F17C2270/0168
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
H01M2250/20
ELECTRICITY
H01M8/04216
ELECTRICITY
F28F7/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B60Y2200/15
PERFORMING OPERATIONS; TRANSPORTING
B60L50/70
PERFORMING OPERATIONS; TRANSPORTING
Y02E60/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02E60/32
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02T90/40
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
H01M8/04082
ELECTRICITY
F17C11/00
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F28F7/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Abstract
The invention relates to a metal hydride hydrogen storage and supply arrangement integrated for use in a fuel cell utility vehicle. The storage arrangement includes a plurality of metal hydride containers suitable to be filled with a metal hydride material, the containers being connectable in parallel to a gas manifold; heat transfer means located between the metal hydride containers; and a filler body located in a space between the metal hydride containers and the heat transfer means.
Claims
1. A metal hydride hydrogen storage arrangement suitable for use as a counterweight in a fuel cell utility vehicle, the storage arrangement including: a plurality of metal hydride containers filled with a metal hydride material, the containers being connectable in parallel to a gas manifold, wherein the metal hydride material has a hydrogen equilibrium pressure in excess of 100 kPa at a temperature of between 50° C. and 60° C., and wherein an operating temperature of the metal hydride material is below its activation temperature; heating and cooling means located between the metal hydride containers; and a filler body formed by the melting and solidification of a metal or an alloy in a space between the metal hydride containers and the heating and cooling means, wherein the filler body adjoins the surfaces of the heating and cooling means and the metal hydride containers to enable heat exchange between the metal hydride containers and the heating and cooling means.
2. The metal hydride hydrogen storage arrangement of claim 1 in which the metal or the alloy used for the filler body has a melting/solidification point below the maximum allowed operation temperature of the metal hydride container, but above the activation temperature of the metal hydride material inside the metal hydride container.
3. The metal hydride hydrogen storage arrangement of claim 2 in which the metal or the alloy which forms the filler body is a lead or a lead alloy with a melting point between 150 and 350° C., thermal conductivity above 35 W/(m.Math.K) and a density above at least 8 kg/L.
4. A method of manufacturing a metal hydride hydrogen storage arrangement suitable for use in a fuel cell utility vehicle, the method including the steps of: locating a plurality of metal hydride containers, filled with a metal hydride material, and heat transfer means inside a casting mould to form a pre-assembly; evacuating an inner space of the containers; filling a space between the containers and the heat transfer means with a filler material by way of a melting and solidification process in which the filler material is heated to a temperature higher than the activation temperature of the metal hydride; allowing the filler material to cool and solidify; and removing the casting mould.
5. The method of claim 4 in which the step of filling the space between the containers and the heat transfer means with a filler material to include the steps of: pre-heating the pre-assembly; filling the space between the containers and the heat transfer means with the filler material; cooling the pre-assembly filled with the filler material to a temperature below the melting/solidification point; stopping the evacuating of the inner volume of the metal hydride containers; filling the inner volume of the metal hydride containers via the gas manifold with a pressurised gas; and cooling the pre-assembly filled with the solidified filler material and the pressurised gas to room temperature.
6. The method of claim 5 in which the pre-assembly of the metal hydride hydrogen storage arrangement may be open at the top, and wherein the pre-heating step is carried out by directing a flow of hot air onto the top of the pre-assembly.
7. The method of claim 5 wherein the step of pre-heating the pre-assembly is continued until reaching a temperature of between a half and two thirds of the melting point of the metal or the alloy which forms the filler body.
8. The method of claim 5 wherein the pressurised gas is hydrogen, an inert gas, or a mixture of hydrogen and an inert gas.
9. The method of claim 5 in which the pressurised gas is not hydrogen, the method in this instance including a final activation procedure which includes the steps of: releasing the pressurised gas from the inner volume of the containers via the gas manifold; evacuating the inner volume of the containers via the gas manifold; and filling the inner volume of the containers with pressurised hydrogen via the gas manifold.
10. A metal hydride hydrogen storage arrangement including a plurality of storage arrangements as described in claim 1.
11. A utility vehicle including a counterweight, characterized in that the counterweight is defined by the metal hydride hydrogen storage arrangement as described in claim 1.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1) One embodiment of the invention will now be described by way of a non-limiting example, with reference to the accompanying drawings in which:
(2)
(3)
(4)
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DETAILED DESCRIPTION OF THE INVENTION
(7) Referring to the drawings, in which like numerals indicate like features, a non-limiting example of a hydrogen storage arrangement in accordance with an embodiment of the invention is generally indicated by reference numeral 10.
(8) The storage arrangement 10, shown in cross-section in
(9) The gas input/output pipelines of the containers 11 are connected to a common gas manifold 12 that terminates in an external pipeline 13, which enables H.sub.2 charging and discharging of the storage arrangement 10 during absorption or desorption in or out of the MH containers, respectively.
(10) Since H.sub.2 absorption in MH is an exothermic process, and H.sub.2 desorption is endothermic, the storage arrangement must include heat transfer means 14 for cooling the MH containers 11 during H.sub.2 charging. The storage arrangement also requires means for heating the containers when discharging H.sub.2. The maximum efficiency of the cooling and the heating is achieved when the heat transfer means (in the form of heating/cooling means 14) are uniformly distributed in between the MH containers 11 in order to provide approximately the same heat transfer distances to the different containers. Although any kind of the heating/cooling means (heat pipes, electric heaters, thermoelectric modules, etc.) can be used within the scope of the invention, in the preferred embodiment, the heating/cooling means 14 is in the form of a tubing for conveying a heating/cooling fluid (e.g., hot and cold water). The heating/cooling means 14 are in flow communication with a supply conduit 15 and a discharge conduit 16.
(11) The space between the metal hydride containers 11 and the heating/cooling means 14 is filled with a metal or an alloy which forms a filler body 17 made of a solidified molten metal or alloy, and which closely adjoins the external surfaces of the MH containers 11 and the heating/cooling means 14. Since the metal hydride storage arrangement simultaneously serves as hydrogen storage medium and as a ballast, the metal or alloy should have a high density to provide maximum weight of the storage arrangement at a minimal volume. The metal or alloy also has to have a high thermal conductivity to maximise the rate of the heat exchange between the MH containers 11 and the heating/cooling means 14.
(12) The filler body 17 envelops all other components of the MH storage arrangement including the MH containers 11, the gas manifold 12 and the heating/cooling means 14. Only the ends, 15 and 16, of the heat transfer conduit 14 and an end 13 of the external pipeline protrudes from the filler body 17. Although this does not have to be the case, this embodiment is preferred due to a number of reasons including the sealing of possible micro-leaks in the pipelines and their joints during formation of the filler body 17. However, other embodiments may include configurations where the filler body only partially envelops other components of the MH storage arrangement. When designing the storage arrangement, criteria determining the size of the filling body/degree of the envelopment include: (i) the weight required to be added to the fuel cell power module, (ii) density of the metal or alloy which forms the filler body; and (iii) space available to the hydrogen storage arrangement. All these criteria can be taken into account during the design stage to yield target dimensions of all the components (11-17) of the storage arrangement.
(13) The most effective way of manufacturing the hydrogen storage arrangement schematically shown in
(14) The use of the “melting-solidification” process, together with properties of the selected MH material and features of the MH container which can be used in the invention, present some limitations as to the selection of the metal or alloy for the filler body. First of all, the melting/solidification point (MP) of the metal or alloy for making the filler body 17 must not be higher than the maximum allowed operation temperature of the MH container 11. Among the materials commonly used for the manufacturing solid state hydrogen storage containers, the maximum allowed operation temperature (Tmax=537° C.) is associated with stainless steel. Accordingly, in a preferred embodiment of the invention stainless steel is used as a material to manufacture the MH containers 11. Since any additional joint (gasket, sealed thread coupling, etc.) reduces the temperature rating, the preference is given to the all-welded stainless steel structure.
(15) The maximum allowed operation temperature (Tmax=537° C. in the case of SS) also limits the metals or alloys which are suitable for casting the filler body 17. For example, copper (MP=1084.6° C.) is not suitable despite its very high thermal conductivity (TC=400 W/(m K)) and relatively high density (8.9 kg/L). The molten copper will end up reducing the strength of the stainless steel containers, which is obviously not desirable.
(16) The inventors have found that one of the most suitable metals for the making the filler body 17 is lead, which combines a high density (11.3 kg/L) with a not too high melting point (327.5° C.). Thermal conductivity of the lead is modest (35 W/(m K)) but it is similar to the most heat conductive stainless steels (TC=12-45 W/(m K)). Further optimisation of the material for making the filler body within the scope of this invention can be done by using lead alloys with tin (minimum MP=183° C. for the alloy containing 37 wt. % Pb and 63 wt. % Sn; TC increases in ˜1.5 times as compared to pure Pb), cadmium (minimum MP=246° C. at 17 wt. % Cd in Pb), antimony (minimum MP=252° C. at 11 wt. % Sb in Pb), or multicomponent lead-containing alloys, like Cerrosafe (Pb 37.7 wt. %, Bi 42.5 wt. %, Sn 11.3 wt. %, Cd 8.5% wt. %; MP=158-190° C.) or Wood's alloy (Pb 26.7 wt. %, Bi 50 wt. %, Sn 13.3 wt. %, Cd 10% wt. %; MP=70° C.). The use of lead alloys with various compositions therefore allows one to vary the melting/solidification point in relatively wide limits. Apart from the melting point, the selection criteria for the lead alloys for making the filler body include its low cost and reasonably high thermal conductivity.
(17) The melting/solidification point of the metal or alloy for making the filler body 17 also has to be higher than the activation temperature of the MH material loaded in the metal hydride containers 11. Importantly, the operating temperature of the MH material must be below its activation temperature, and the H.sub.2 equilibrium pressure for the MH material at the operating temperature must be higher than the atmospheric pressure to provide H.sub.2 supply to a fuel cell stack.
(18) Summarising the above-mentioned, in the preferred embodiment of this invention, the material for making the filler body 17 is lead or a lead-containing alloy with melting/solidification point between 150 and 350° C., and the activation temperature of the metal hydride material is between 100 and 300° C. Most of the commonly used hydrogen storage alloys (e.g. AB.sub.5- and AB.sub.2-type) satisfy the latter criterion. Moreover, at the temperatures of 50-60° C. (typical operating temperature of low-temperature PEM fuel cell which can be thermally coupled with the MH storage, many of these alloys have a hydrogen equilibrium pressure in excess of 1 bar (100 kPa), which makes them suitable for the use in this invention.
(19) As mentioned above, in the manufacturing of the MH hydrogen storage arrangement in accordance with the present invention entails a procedure of forming the filler body 17 by the use of “melting-solidification” route. This procedure is crucial, and the method of manufacturing the MH storage arrangement by way of this procedure is described below. (a) The first step in the manufacturing of the MH storage arrangement entails the assembly of all its components (MH containers, heating/cooling means, gas manifold), except for the filler body, and the placement of such components in a shell or casting mould which, together with the components (MH containers, heating/cooling means, gas manifold), forms a pre-assembly of the metal hydride hydrogen storage arrangement. The MH containers and the heating/cooling means are first installed in their positions in the storage arrangement, followed by the installation of the gas manifold. Leak tests are then performed to test the integrity of the system. (b) The pre-assembly, as constructed above, is then located at the place where the casting/filling step will take place. This process requires heating of the assembly to elevated temperatures. Considering that all metal hydride materials are sensitive to a number of gas species (including oxygen and water vapours) that can remain in the inner space of the MH containers or desorb from the surface of the MH material during heating, the inner space of the containers must be evacuated at all times during the manufacturing process in order to avoid a loss or reduction of hydrogen sorption properties of the MH material due to its interaction with the gas species at elevated temperatures. In addition, the evacuation during the heating process will promote the activation of the MH material, so as to enable it to absorb and desorb hydrogen.
(20) If the gas with which the MH containers are filled during stage (f) is not pure hydrogen, the storage arrangement should also be subjected to the following final activation procedure: (a) Release of the pressurised gas from the inner volume of the MH containers via the gas manifold. This can be done by opening the valve 32 in any position after disconnecting the same from the vacuum and gas supply lines. This should be done before the storage arrangement is removed from the shell/casting during step (f) above. After performing this procedure, the storage arrangement (and more particularly the MH containers) has to be connected to a final activation setup, the piping diagram of which is similar to the gas piping shown in
(21) The MH storage arrangement and the method of manufacturing thereof as described above can be made as a single unit ready for integration into a utility vehicle. Alternatively, the storage arrangement can be made up of an assembly of several smaller modules made as described above. This option adds flexibility in making MH hydrogen storage arrangements for various utility vehicles based on a unified modular design that is beneficial for mass production.
EXAMPLE
(22) The following example illustrates one of numerous embodiments of the present invention.
(23) According to the design specification of a 15 kWe fuel cell power module for a 3.5 tonnes STILL electric forklift, a metal hydride hydrogen storage arrangement should: provide hydrogen storage capacity of 20 Nm.sup.3 H.sub.2; have a weight between 1 and 1.5 tonnes; occupy a volume not higher than 200 L; and not be longer than 1 m.
(24) For the hydrogen storage arrangement, it was suggested to use 40 tubular metal hydride containers made as all-welded stainless steel structures, which will in use be filled with an AB.sub.2-type hydrogen storage alloy characterised by a hydrogen equilibrium pressure of about 10 bar at room temperature and an activation temperature of between 150 and 300° C. Each container is 51.3 mm in diameter, 800 mm in length, 8.9 kg in weight (incl. MH material) and has a hydrogen storage capacity of about 0.5 Nm.sup.3.
(25) The assembly of the 40 MH containers staggered into a 200 L volume will have a weight of 356 kg. Had the empty space between containers been filled with water (as per one of the prior art configurations), the total weight of the hydrogen storage arrangement would have amounted to about 490 kg, which is far below the lower weight constraint of the application.
(26) In order to adhere to the specification requirements, a metal hydride hydrogen storage arrangement according to the present invention has been designed. The storage arrangement is an assembly of 8 modules (MH cassettes) each comprising of 5 MH containers as described above. A 15 mm OD stainless steel heating/cooling pipe extends between the cassettes and the empty space is occupied by a filler body made of lead. The total storage arrangement dimensions (8 cassettes packed together) are 704 mm (L)×960 mm (W)×264 mm (H) that corresponds to the total volume below 170 L. The target weight of one cassette was calculated to be between 125 and 187.5 kg, with the combined weight therefore exceeding the 1 ton requirement.
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(29) Before depositing the lead filler, the assembly was evacuated. After achieving a vacuum of about 10.sup.−2 mbar, the assembly was pre-heated up to about 170° C. (temperature measurement by a K-type thermocouple built into cassette, also assisted by optical pyrometer). The pre-melted lead (T˜350° C.) was then casted into the pre-assembly. During pre-heating (20 min) and casting the molten lead (30 min) the pressure in the evacuated system increased to 2 mbar followed by the gradual decrease to 0.1 mbar before the end of the casting step.
(30) After finishing the lead casting, the heaters were switched off, and the lead-filled cassette was allowed to cool down to a temperature of about 90° C., at which point the vacuum was in excess of 5.10.sup.−2 mbar. The cassette was then filled with pressurised argon at a pressure of about 50 bar.
(31) After cooling the lead encased and argon-filled cassette to room temperature, the stainless steel sheets making up the shell 18 were removed, and the module of the metal hydride hydrogen storage arrangement (960×269×88 mm; weight 144 kg) was connected to a final activation setup. During final activation, the argon was first released, and the containers where then again evacuated to about 3.10.sup.−2 mbar. Hydrogen at a supply pressure of about 50 bar was then supplied to the gas manifold 12. Hydrogen absorption in the MH started immediately, as was evident from the gradual increase of the temperature of the storage arrangement measured by a built-in K-type thermocouple 19. The hydrogen was introduced at maximum H.sub.2 flow, which in this case was 40 NL/min (upper limit set by mass flow controller due to necessity to be within its measurement range). The H.sub.2 flow of 40 NL/min remained unchanged during 40 minutes followed by a gradual decrease in flowrate when the temperature reached about 60° C. (increased from an initial temperature of 25° C.). After the cooling of the storage arrangement commenced (using water at a temperature of about 20° C. and a flow rate of about 5 L/min), the flow of the absorbed H.sub.2 (40 NL/min) increased again, and remained constant for a further 10 min followed by a gradual decrease. The total amount of hydrogen absorbed in the storage arrangement during 100 minutes (until the H.sub.2 flow rate decreased below 4 NL/min) was of 2591 NL (calculated by the integration of time dependence of the flow rate). This was more than the specification requirement (2500 NL).
(32) The example presented above demonstrates the workability of the engineering solution described in the present invention even in the case where the best possible embodiment could not be used (due to the incomplete encapsulation of the storage arrangement components within the filler body, use of argon instead of hydrogen to fill the inner volume of the MH containers after its solidification, and the modest heat conductivity of the metal used).
(33) The inventors foresee that the practical application of the invention can be further improved by the optimisation of the composition of the alloy forming the filler body (increase of the thermal conductivity without a significant decrease of the density and increase in the cost), and the improvement of the design of the storage arrangement and the auxiliary accessories (casting mould, top heater), etc.
(34) The present invention offers a design and a method of manufacturing a compact hydrogen storage arrangement which will be useful in a number of fuel cell powered heavy duty vehicles including material handling units, mining locomotives, and marine applications. The use of the invention will also result in the reduction or elimination of space occupied by ballast in these kind of vehicles, thus adding flexibility to the layout of other components (stack+BoP) of the fuel cell power modules which can in turn be improved in terms of ease of assembly and service.
(35) The solution of the problem of the increase of space available for the placement of a fuel cell and its BoP within weight and space constrains of a utility vehicle resides in “merging” the ballast and the metal hydride hydrogen storage system in an integrated design resulting in a unified hydrogen storage arrangement. The invention is inventive, in that it departs from the conventional design methodology of MH storage systems, in which the aim is to reduce the weight of the fuel storage arrangements. At the same time, the integrated system will also provide efficient heating and cooling of the MH material to provide sufficient rates of H.sub.2 desorption/absorption during the H.sub.2 discharge/charge. Finally, the procedure of making the MH hydrogen storage arrangement has to be simple, cost-efficient, safe and reliable—including the elimination of a possibility of deterioration of hydrogen sorption properties of the MH material during the manufacturing of the storage arrangement. The present invention meets all these criteria.
(36) It will be appreciated that the above is only one embodiment of the invention and that there may be many variations without departing from the spirit and/or the scope of the invention. It is easily understood from the present application that the particular features of the present invention, as generally described and illustrated in the figures, can be arranged and designed according to a wide variety of different configurations. In this way, the description of the present invention and the related figures are not provided to limit the scope of the invention but simply represent selected embodiments.
(37) The skilled person will understand that the technical characteristics of a given embodiment can in fact be combined with characteristics of another embodiment, unless otherwise expressed or it is evident that these characteristics are incompatible. Also, the technical characteristics described in a given embodiment can be isolated from the other characteristics of this embodiment unless otherwise expressed.