CA2368437C - Metalliferous storage material for hydrogen and method for producing same - Google Patents
Metalliferous storage material for hydrogen and method for producing same Download PDFInfo
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- CA2368437C CA2368437C CA002368437A CA2368437A CA2368437C CA 2368437 C CA2368437 C CA 2368437C CA 002368437 A CA002368437 A CA 002368437A CA 2368437 A CA2368437 A CA 2368437A CA 2368437 C CA2368437 C CA 2368437C
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
- C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
- C01B3/001—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes characterised by the uptaking media; Treatment thereof
- C01B3/0018—Inorganic elements or compounds, e.g. oxides, nitrides, borohydrides or zeolites; Solutions thereof
- C01B3/0026—Metals or metal hydrides
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/24—Electrodes for alkaline accumulators
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- H01M4/00—Electrodes
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- H01M4/24—Electrodes for alkaline accumulators
- H01M4/242—Hydrogen storage electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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Abstract
The invention relates to a metalliferous material and a method for producing the same. The metalliferous material contains at least one metal oxide as catalyst means for the hydrogenation or dehydrogenation of said metalliferous material. According to the inventive method for producing such a metalliferous material, i.e. the actual storage material, the metalliferous material and/or the catalyst means are subjected to a mechanic milling process.
Description
METALLIFERROUS STORAGE MATERIAL FOR HYDROGEN AND METHOD FOR
PRODUCING SAME
Description The invention relates to a metalliferrous material and a method of producing the material.
It is first pointed out that, under the term metallifer-rous material, atomic metals, metal alloys, intermetallic phases of metals or compound materials as well as corresponding hydrides are to be understood.
It is known that, on the basis of reversible metal hy-drides, hydrogen storage devices, so-called hydride storage de-vices, can be formed. The storage device can be charged while heat is released, that is, hydrogen is bound by chemo-sorption and discharged by the application of heat. Hydrogen storage devices can therefore be excellent energy storage devices for mobile and/or stationary applications. They might form in the future a notable storage potential since no noxious emissions are released during the discharge of the hydrogen storage de-vices.
Very suitable for such hydride storage devices are the so-called mono-crystalline hydrides, which are capable of rapidly storing and releasing the hydrogen. Their manufacture however has been very expensive, so far. Their manufacture, so far, has involved high-energy grinding of elemental components or pre-alloys of nano-crystalline alloys, wherein the grinding procedure can be very lorig. In a final process step, these nano-crystalline alloys were subjected, depending on the condi-tions, to a multistage heat treatment under a high hydrogen pressure to be hydrogenated thereby. For many alloys, further-more, a multiple charging and discharging with hydrogen is nec-essary to achieve full capacity.
Alternatively, it has been tried to synthesize the respec-tive hydrides by grinding in a hydrogen atmosphere or in a pure chemical way. It has beerL found, however, that, in this way, the yield of the desired hydrides is smaller and partially ad-ditional undesirable phases occur.
Furthermore, certain phases could, or respectively can, not be formed with the known conventional methods.
The German patent application No. 197 58 384.6 discloses a method for the manufacture of nano-crystalline metal hydrides with which the manufacture of stable and meta-stable hydrides or hydride-meta-stable alloys is possible with a very high yield of up to 100%. The method described in the mentioned German patent application can be performed with easily control-lable limiting conditions and with a relativel.y small energy consumption.
In order for such a hydrogen storage device to rapidly provide the energy stored therein when needed and to permit rapid charging of the hydrogeri storage device, it is desirable that the reaction speed duririg hydrating and dehydrating of metals at low temperatures is kept very high that is a very high reaction speed is to be aimed at.
To this end, so for, the reaction surface has been in-creased by reducing the size of the par.ticles / crystals of the materials to be hydrogenated or dehydr.ogenated as far as this was technically feasible. Other ineans for increasing the reac-tion speed included the addition of nickel, platinum or palla-dium.
The disadvantage of the measures known so far for increas-ing the reaction speed during the hydrogenation and particu-larly the dehydrogenation, that is, the delivery of the hydro-gen from the hydrogen starage device is that the available speeds are in-sufficient for hydrogen storage devices intended for technical applications.
It is therefore the object of the present application to provide a metalliferrous material, such as a metal, a metal al-loy or an intermetallic phase, compound materials of metals as well as corresponding hydrides with which, during hydrogenation and dehydrogenation, the reaction speeds are so high, that they are technically feasible for use as energy storage devices. A
method is to be provided by which the manufacture of a metal-liferrous material such as a metal, a metal alloy, an intermet-allic phase or a compound material of the materials or corre-sponding hydrides can be performed in a simple and inexpensive way such that metals manufactured in this way can be used com-mercially as hydrogen storage devices in a cost-effective man-ner and with the technically necessary high reaction speed dur-ing hydrogenation and dehydrogeriation.
PRODUCING SAME
Description The invention relates to a metalliferrous material and a method of producing the material.
It is first pointed out that, under the term metallifer-rous material, atomic metals, metal alloys, intermetallic phases of metals or compound materials as well as corresponding hydrides are to be understood.
It is known that, on the basis of reversible metal hy-drides, hydrogen storage devices, so-called hydride storage de-vices, can be formed. The storage device can be charged while heat is released, that is, hydrogen is bound by chemo-sorption and discharged by the application of heat. Hydrogen storage devices can therefore be excellent energy storage devices for mobile and/or stationary applications. They might form in the future a notable storage potential since no noxious emissions are released during the discharge of the hydrogen storage de-vices.
Very suitable for such hydride storage devices are the so-called mono-crystalline hydrides, which are capable of rapidly storing and releasing the hydrogen. Their manufacture however has been very expensive, so far. Their manufacture, so far, has involved high-energy grinding of elemental components or pre-alloys of nano-crystalline alloys, wherein the grinding procedure can be very lorig. In a final process step, these nano-crystalline alloys were subjected, depending on the condi-tions, to a multistage heat treatment under a high hydrogen pressure to be hydrogenated thereby. For many alloys, further-more, a multiple charging and discharging with hydrogen is nec-essary to achieve full capacity.
Alternatively, it has been tried to synthesize the respec-tive hydrides by grinding in a hydrogen atmosphere or in a pure chemical way. It has beerL found, however, that, in this way, the yield of the desired hydrides is smaller and partially ad-ditional undesirable phases occur.
Furthermore, certain phases could, or respectively can, not be formed with the known conventional methods.
The German patent application No. 197 58 384.6 discloses a method for the manufacture of nano-crystalline metal hydrides with which the manufacture of stable and meta-stable hydrides or hydride-meta-stable alloys is possible with a very high yield of up to 100%. The method described in the mentioned German patent application can be performed with easily control-lable limiting conditions and with a relativel.y small energy consumption.
In order for such a hydrogen storage device to rapidly provide the energy stored therein when needed and to permit rapid charging of the hydrogeri storage device, it is desirable that the reaction speed duririg hydrating and dehydrating of metals at low temperatures is kept very high that is a very high reaction speed is to be aimed at.
To this end, so for, the reaction surface has been in-creased by reducing the size of the par.ticles / crystals of the materials to be hydrogenated or dehydr.ogenated as far as this was technically feasible. Other ineans for increasing the reac-tion speed included the addition of nickel, platinum or palla-dium.
The disadvantage of the measures known so far for increas-ing the reaction speed during the hydrogenation and particu-larly the dehydrogenation, that is, the delivery of the hydro-gen from the hydrogen starage device is that the available speeds are in-sufficient for hydrogen storage devices intended for technical applications.
It is therefore the object of the present application to provide a metalliferrous material, such as a metal, a metal al-loy or an intermetallic phase, compound materials of metals as well as corresponding hydrides with which, during hydrogenation and dehydrogenation, the reaction speeds are so high, that they are technically feasible for use as energy storage devices. A
method is to be provided by which the manufacture of a metal-liferrous material such as a metal, a metal alloy, an intermet-allic phase or a compound material of the materials or corre-sponding hydrides can be performed in a simple and inexpensive way such that metals manufactured in this way can be used com-mercially as hydrogen storage devices in a cost-effective man-ner and with the technically necessary high reaction speed dur-ing hydrogenation and dehydrogeriation.
The object is solved with regard to the metal-containing material in that it includes a metal oxide as catalyst for the hydrogenation or dehydrogetiation thereof.
In accordance with the invention, the fact is utilized that, in comparison with pure metals, metal oxides are brittle, whereby a smaller particle size and a homogeneous distribution of the metal oxide in the material is achieved. As a result, the reaction kinetics are substanl:ially increased in comparison with metallic catalysts. Another advantage is that the metal oxides are available as catalysts generally at much lower prices than metals or respectively, metal alloys so that also the aim of commercial utilization at reasonable costs for the metalliferous materials according to the inventioa can be achieved.
Basically, the metal oxide is an oxide of atomic metals such as the oxide of the metals Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Ce, Mo, Sn, La, Hf, Ta, W.
In accordance with an advantageous embodiment of the invention, the metal oxide may also consist of mixed oxides of the metals, particularly of the metals listed earlier or of mixtures of the metal oxides.
Advantageously, the metal oxide or metal oxides may be formed by rare eartb metals or metal oxides or mixtures of rare earth metals.
In an advantageous embodiment of the invention, the metal has a nano-crystalline structure, wherein, equally advanta-geously, also the catalyst has a nano-crystalline structure.
If the metal and/or the catalyst have a crystalline structure, the reaction surface and, consequently, the reaction speed of the hydrogenation or, respectively, the dehydrogenation of the metalliferrous material are increased.
The method according to the invention for the manufacture of such a metalliferrous material is characterized in that the metalliferrous material and/or the catalyst are subjected to a mechanical grinding procedure with the object to form, from both components, a powder with an optimized reaction surface of the metalliferrous material as well as a uniform distribution of the catalyst.
The grinding procedure itself may be selected, depending on the metalliferrous mateL=ial. and/or the catalyst, to be dif-ferently long so as to achieve the optimal desired reaction surface and an optimal distribution of the catalyst of the met-alliferous material according to the invention. In this connec-tion, it may be advantageous if the metalliferous material as such is first subjected to the grinding and the catalyst is added subsequently to the grinding process, however the process may be reversed, that is, the catalyst may be first subjected to the grinding followed by the metalliferous material. Also, these distinguished possible procedures for the grinding are selected depending on the nietal.liferous materials and depending on the catalyst to be added.
In order to prevent reactions with the ambient gas during thr grinding of the metaliferous material (metal, metal alloy, intermetallic phase, compound material as well as the hydrides thereof) the method is preferably performed under an inert at-mosphere wherein the inert gas is preferably argon.
As already mentioned, the duration of the grinding process for a metalliferous material (metal, metal alloy, intermetallic phase, compound material as well as the hydrides thereof) and the catalyst is variably selectable depending on the metallif-erous material and the selected catalyst. Preferably, the du-ration of the grinding process is in the area of 1 to 200 hours.
In another type of the method for the manufacture of a metalliferous material, which may be used as electrode material at least for secondary elements, at least one metal oxide is formed on the surface of the electrode material in situ by con-tact with oxygen from elements of the electrode/material or by direct supply of oxygen. In this way, a catalyzing oxide can be formed in situ from elements of the hydride storage mate-rial.
Preferably, during performance of the method, the surface of the electrode material is activated chemically and/or me-chanically before the oxide is formed, whereby the oxide forma-tion of the metal can be improved.
The invention will now be described in detail with refer-ence to various diagrams, which describe the hydrogenation and dehydrogenation behavior as well as other important parameters.
It is shown in:
Fig. 1 an x-ray diffraction diagram after a grinding dura-tion of the metalliferous material of one hour and 200 hours, Fig. 2a a representatiotl of the sorption behavior of the metalliferous material for the representation of the charging temperature and the charging speed with hydrogen;
Fig. 2b the sorption behavior of the metalliferous mate-rial at another temperature depending on the charging time, Fig. 2c a pressure curve with magnesium-hydrogen for the representation of a maximal hydrogen content of the metallifer-ous material, s Fig. 3 X-ray diffraction curves showing the catalyst CrZO3 in the hydrated as well as in Lhe dehydrated state arid also traces of MgO and Cr, Fig. 4a-4d a representation of the improvement of the ki-netics during the absorption of hydrogen as well as its desorp-tion, Fig. 5 a typical pattern for the charging capacity during the first 30 charge and dischar,qe cycles of an untreated A85 hydride alloy, Fig. 6 the representation of an activation after the first 5 cycles to show an insufficient activation, Fig. 7 a pattern according to Fig. 5 catalyzed however with a metal oxide according to t_he invention, Fig. 8 a pattern accordinq to Fig. 6 catalyzed however with a metal oxide according to the invention, Fig. 9 a pattern for the discharge capacity achievable with an untreated alloy in the 10. cycle as a function of the discharge currents applied (with respect to lg alloy), Fig. 10 a representation according to Fig. 9, but in the 30'h cycle, Fig. 11 a corresponding paLtern for the same alloy as in Fig. 9, however, catalyzed with a metal oxide according to the invention, and S Fig. 12 a corresponding paLLern for the same alloy as in Fig. 10, but catalyzed with a metal oxide according to the in-vention.
The metalliferous material of the invention may comprise to various metals, metal alJoys, intermetallic phases, compound materials and corresponding hydrides. They form the storage material of the hydrogen storage devices according to the in-vention. To accelerate the hydrogenation or the dehydrogena-tion metal oxides are added as catalysts to these metalliforins 15 materials, wherein the metal oxide may also be a mixed oxide, that is, it may include several metal oxides. Metal oxides, or, respectively, mixed oxides may consist for example of Mg, A1, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Sn, Ce, La, Hf, Ta, W or of rare earth. The above listing 20 however is not to be understood in such a way that it repre-sents a limitation of the metal oxides according to the inven-tion to oxides of these metals. Oxides of metals may be for A1203, TiO2, V2O51 Cr203, Fe203, Fe?O4r CuO, Nb2O,, MoO, MoOz, etc. The catalyst may also have a nano-crystalline structure.
A method for the manufacture of a metalliferous material according to the invention will be described on the basis of an example. In the description reference is made to the figures.
In accordance with the invention, the fact is utilized that, in comparison with pure metals, metal oxides are brittle, whereby a smaller particle size and a homogeneous distribution of the metal oxide in the material is achieved. As a result, the reaction kinetics are substanl:ially increased in comparison with metallic catalysts. Another advantage is that the metal oxides are available as catalysts generally at much lower prices than metals or respectively, metal alloys so that also the aim of commercial utilization at reasonable costs for the metalliferous materials according to the inventioa can be achieved.
Basically, the metal oxide is an oxide of atomic metals such as the oxide of the metals Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Ce, Mo, Sn, La, Hf, Ta, W.
In accordance with an advantageous embodiment of the invention, the metal oxide may also consist of mixed oxides of the metals, particularly of the metals listed earlier or of mixtures of the metal oxides.
Advantageously, the metal oxide or metal oxides may be formed by rare eartb metals or metal oxides or mixtures of rare earth metals.
In an advantageous embodiment of the invention, the metal has a nano-crystalline structure, wherein, equally advanta-geously, also the catalyst has a nano-crystalline structure.
If the metal and/or the catalyst have a crystalline structure, the reaction surface and, consequently, the reaction speed of the hydrogenation or, respectively, the dehydrogenation of the metalliferrous material are increased.
The method according to the invention for the manufacture of such a metalliferrous material is characterized in that the metalliferrous material and/or the catalyst are subjected to a mechanical grinding procedure with the object to form, from both components, a powder with an optimized reaction surface of the metalliferrous material as well as a uniform distribution of the catalyst.
The grinding procedure itself may be selected, depending on the metalliferrous mateL=ial. and/or the catalyst, to be dif-ferently long so as to achieve the optimal desired reaction surface and an optimal distribution of the catalyst of the met-alliferous material according to the invention. In this connec-tion, it may be advantageous if the metalliferous material as such is first subjected to the grinding and the catalyst is added subsequently to the grinding process, however the process may be reversed, that is, the catalyst may be first subjected to the grinding followed by the metalliferous material. Also, these distinguished possible procedures for the grinding are selected depending on the nietal.liferous materials and depending on the catalyst to be added.
In order to prevent reactions with the ambient gas during thr grinding of the metaliferous material (metal, metal alloy, intermetallic phase, compound material as well as the hydrides thereof) the method is preferably performed under an inert at-mosphere wherein the inert gas is preferably argon.
As already mentioned, the duration of the grinding process for a metalliferous material (metal, metal alloy, intermetallic phase, compound material as well as the hydrides thereof) and the catalyst is variably selectable depending on the metallif-erous material and the selected catalyst. Preferably, the du-ration of the grinding process is in the area of 1 to 200 hours.
In another type of the method for the manufacture of a metalliferous material, which may be used as electrode material at least for secondary elements, at least one metal oxide is formed on the surface of the electrode material in situ by con-tact with oxygen from elements of the electrode/material or by direct supply of oxygen. In this way, a catalyzing oxide can be formed in situ from elements of the hydride storage mate-rial.
Preferably, during performance of the method, the surface of the electrode material is activated chemically and/or me-chanically before the oxide is formed, whereby the oxide forma-tion of the metal can be improved.
The invention will now be described in detail with refer-ence to various diagrams, which describe the hydrogenation and dehydrogenation behavior as well as other important parameters.
It is shown in:
Fig. 1 an x-ray diffraction diagram after a grinding dura-tion of the metalliferous material of one hour and 200 hours, Fig. 2a a representatiotl of the sorption behavior of the metalliferous material for the representation of the charging temperature and the charging speed with hydrogen;
Fig. 2b the sorption behavior of the metalliferous mate-rial at another temperature depending on the charging time, Fig. 2c a pressure curve with magnesium-hydrogen for the representation of a maximal hydrogen content of the metallifer-ous material, s Fig. 3 X-ray diffraction curves showing the catalyst CrZO3 in the hydrated as well as in Lhe dehydrated state arid also traces of MgO and Cr, Fig. 4a-4d a representation of the improvement of the ki-netics during the absorption of hydrogen as well as its desorp-tion, Fig. 5 a typical pattern for the charging capacity during the first 30 charge and dischar,qe cycles of an untreated A85 hydride alloy, Fig. 6 the representation of an activation after the first 5 cycles to show an insufficient activation, Fig. 7 a pattern according to Fig. 5 catalyzed however with a metal oxide according to t_he invention, Fig. 8 a pattern accordinq to Fig. 6 catalyzed however with a metal oxide according to the invention, Fig. 9 a pattern for the discharge capacity achievable with an untreated alloy in the 10. cycle as a function of the discharge currents applied (with respect to lg alloy), Fig. 10 a representation according to Fig. 9, but in the 30'h cycle, Fig. 11 a corresponding paLtern for the same alloy as in Fig. 9, however, catalyzed with a metal oxide according to the invention, and S Fig. 12 a corresponding paLLern for the same alloy as in Fig. 10, but catalyzed with a metal oxide according to the in-vention.
The metalliferous material of the invention may comprise to various metals, metal alJoys, intermetallic phases, compound materials and corresponding hydrides. They form the storage material of the hydrogen storage devices according to the in-vention. To accelerate the hydrogenation or the dehydrogena-tion metal oxides are added as catalysts to these metalliforins 15 materials, wherein the metal oxide may also be a mixed oxide, that is, it may include several metal oxides. Metal oxides, or, respectively, mixed oxides may consist for example of Mg, A1, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Sn, Ce, La, Hf, Ta, W or of rare earth. The above listing 20 however is not to be understood in such a way that it repre-sents a limitation of the metal oxides according to the inven-tion to oxides of these metals. Oxides of metals may be for A1203, TiO2, V2O51 Cr203, Fe203, Fe?O4r CuO, Nb2O,, MoO, MoOz, etc. The catalyst may also have a nano-crystalline structure.
A method for the manufacture of a metalliferous material according to the invention will be described on the basis of an example. In the description reference is made to the figures.
Examples:
MgH1 + 5Cr?O.5 5 Experimental particulars: 30.7g MgHz and 9.3g Cr1o, were placed into a 250 ml grinding coiitainer of steel. 400g steel balls (ball diameter 10mm, ratio powder : balls = 1:10) were added.
The powder was subjected to a mechanical high-energy grinding process in a planetary ball aLill of the type "Fritsch Pulver-isette 5". The grinding process was performed under an argon atmosphere for all together 200 hours. During and after the grinding process small amounts of powder were removed for an X-ray structure analysis. Fig. 1 shows the x-ray diffraction diagrams after a grinding duration of 1 hr and 200 hrs. in ad-dition to the MgH2 also the Cr;zOj is detectable after 200 hrs by x-ray structure analysis.
Sorption Behavior: In accordance with Fig. 1, the material can be charged at a temperattlre of 300"C in 100 sec with 4 wt%
hydrogen. At a temperature T = 250"C, a hydrogen content of about 3.6 wt% is reached already after about 50 sec. Also, at T=100 C, a rapid charging is possible. A complete hydrogen discharge is possible at T = 300"C in about 400 sec. At T=
250 C, however, in 1200 sec (see Fig. 2b) . In the PCT diagram (Fig. 2c) , a maximal hydrogen cori =Lent of the material of 5 wt%
is shown in addition to the pressure level of 1.6 bar, which can be assigned to the system magnesium-hydrogen. Fig. 3 shows x-ray diffraction pictures in which, in addition, to Cr2031 traces of MgO and eventually Cr as inactive phase are shown in the hydrated as well as in the dchydrated state. Furthermore, MgIH2 can be found in the hydrated and Mg can be found in the dehydrated state.
MgH1 + 5Cr?O.5 5 Experimental particulars: 30.7g MgHz and 9.3g Cr1o, were placed into a 250 ml grinding coiitainer of steel. 400g steel balls (ball diameter 10mm, ratio powder : balls = 1:10) were added.
The powder was subjected to a mechanical high-energy grinding process in a planetary ball aLill of the type "Fritsch Pulver-isette 5". The grinding process was performed under an argon atmosphere for all together 200 hours. During and after the grinding process small amounts of powder were removed for an X-ray structure analysis. Fig. 1 shows the x-ray diffraction diagrams after a grinding duration of 1 hr and 200 hrs. in ad-dition to the MgH2 also the Cr;zOj is detectable after 200 hrs by x-ray structure analysis.
Sorption Behavior: In accordance with Fig. 1, the material can be charged at a temperattlre of 300"C in 100 sec with 4 wt%
hydrogen. At a temperature T = 250"C, a hydrogen content of about 3.6 wt% is reached already after about 50 sec. Also, at T=100 C, a rapid charging is possible. A complete hydrogen discharge is possible at T = 300"C in about 400 sec. At T=
250 C, however, in 1200 sec (see Fig. 2b) . In the PCT diagram (Fig. 2c) , a maximal hydrogen cori =Lent of the material of 5 wt%
is shown in addition to the pressure level of 1.6 bar, which can be assigned to the system magnesium-hydrogen. Fig. 3 shows x-ray diffraction pictures in which, in addition, to Cr2031 traces of MgO and eventually Cr as inactive phase are shown in the hydrated as well as in the dchydrated state. Furthermore, MgIH2 can be found in the hydrated and Mg can be found in the dehydrated state.
Comparison of magnesium + chromium oxide with pure magnesium:
In accordance with Figs. 4a - 4d a clear improvement of the kinetics during absorption of hydrogen as well as during its desorption is apparent. The samples subjected to the saine grinding process have different total capacities of hydrogen.
95 MgH2 + 5 Cr2Q3 can store 5 wt % and 100 MgH2 can store 7.6 wtt hydrogen. This is shown in the PCT diagrams (Fig. 4c).
Fig, 4a shows an increase of the absorption speed at T=300 C by the factor 10. During desorption at the same temperature a speed advantage with a factor of 6 is achieved (Fig. 4b). The material can be fully dehydrated at T = 250'C in about 1200 sec, if the catalyst Cr203 is added (Fig. 4d) . Pure MgHz cannot be dehydrated at T= 250"C within a reasonable period.
With reference to Figs. 5 to 12, it is apparent that the acceleration obtainable in accordance with the invention for storing the hydrogen and for the release from the storage mate-rial of the electrode (anode) of the accumulator as well as the manufacturing method according to the invention substantially increases the power density and the current density of the ac-cumulator by use of the electrode material, which has been catalyzed in accordance with the invention in comparzsoin with conventional accumulators. As a result, the accumulators ac-cording to the invention are suitable for high power applica-tions, for which, so far, only Ni-Cad elements or cells could be used,. Further-more, storage materials carl be used for the electrode whose equilibrium pressure is lower at the application conditions and which form more stable hydrides than those that have been com-mon so far. As a result, lower self-di.scharge rates are achieved. The accelera-tion of the kinetics achieved by the catalysts according to the invention compensates for the loss in thermodynamic drive force . . ~ ) toward a hydrogenation/dehydrogenation of the electrode mate-rial, so that, in spite of the greater stability of the hy-dride, current densities are achieved which are sufficient for the application. The oxide catalyst according to the invention or, respectively, the catalyst additions can be manufactured or provided at substantially lower costs than the metals used so far. The activation proce-dure for the electrode material used so far is elim.inated with the manufacture of the metalliferous electrode material accord-ing to the invention.
It is apparent from figures 5 to 12 that the charging and discharging behavior of the electrode material according to the invention provides for extraordinarily large advantages and im-provements when compared with the corresponding behavior of the conventional electrode materials.
it is basically possible to use the electrode material ac-cording to the invention also for electrodes of non-rechargeable primary elements or cells, which however could be regenerated.
~t
In accordance with Figs. 4a - 4d a clear improvement of the kinetics during absorption of hydrogen as well as during its desorption is apparent. The samples subjected to the saine grinding process have different total capacities of hydrogen.
95 MgH2 + 5 Cr2Q3 can store 5 wt % and 100 MgH2 can store 7.6 wtt hydrogen. This is shown in the PCT diagrams (Fig. 4c).
Fig, 4a shows an increase of the absorption speed at T=300 C by the factor 10. During desorption at the same temperature a speed advantage with a factor of 6 is achieved (Fig. 4b). The material can be fully dehydrated at T = 250'C in about 1200 sec, if the catalyst Cr203 is added (Fig. 4d) . Pure MgHz cannot be dehydrated at T= 250"C within a reasonable period.
With reference to Figs. 5 to 12, it is apparent that the acceleration obtainable in accordance with the invention for storing the hydrogen and for the release from the storage mate-rial of the electrode (anode) of the accumulator as well as the manufacturing method according to the invention substantially increases the power density and the current density of the ac-cumulator by use of the electrode material, which has been catalyzed in accordance with the invention in comparzsoin with conventional accumulators. As a result, the accumulators ac-cording to the invention are suitable for high power applica-tions, for which, so far, only Ni-Cad elements or cells could be used,. Further-more, storage materials carl be used for the electrode whose equilibrium pressure is lower at the application conditions and which form more stable hydrides than those that have been com-mon so far. As a result, lower self-di.scharge rates are achieved. The accelera-tion of the kinetics achieved by the catalysts according to the invention compensates for the loss in thermodynamic drive force . . ~ ) toward a hydrogenation/dehydrogenation of the electrode mate-rial, so that, in spite of the greater stability of the hy-dride, current densities are achieved which are sufficient for the application. The oxide catalyst according to the invention or, respectively, the catalyst additions can be manufactured or provided at substantially lower costs than the metals used so far. The activation proce-dure for the electrode material used so far is elim.inated with the manufacture of the metalliferous electrode material accord-ing to the invention.
It is apparent from figures 5 to 12 that the charging and discharging behavior of the electrode material according to the invention provides for extraordinarily large advantages and im-provements when compared with the corresponding behavior of the conventional electrode materials.
it is basically possible to use the electrode material ac-cording to the invention also for electrodes of non-rechargeable primary elements or cells, which however could be regenerated.
~t
Claims (13)
1. A metalliferous storage material for hydrogen including a metal oxide as catalyst for the hydrogenation or dehydrogenation of the metalliferous storage material, said metal oxide of said catalyst including as the metal at least one selected from the group consisting of Ti, V, Cr, Mn, Fe and Nb, wherein said metal oxide of said catalyst has a nanocrystalline structure.
2. A metalliferous storage material according to claim 1, wherein said metal oxide is a mixed oxide.
3. A metalliferous storage material according to claim 1, wherein said metal has a nanocrystalline structure.
4. A method of producing a metalliferous storage material according to claim 1, said method comprising the step of subjecting the metalliferous material and said catalyst to a mechanical grinding process.
5. A method according to claim 4, wherein said grinding process is performed for a predetermined time.
6. A method according to claim 4, wherein said metalliferous material is first subjected to said grinding process and said catalyst is subsequently added to said grinding process.
7. A method according to claim 4, wherein said catalyst is first subjected to said grinding process and said metalliferous material is subsequently added to said grinding process.
8. A method according to claim 4, wherein said grinding process is performed in a protective inert gas atmosphere.
9. A method according to claim 8, wherein said inert gas is argon.
10. A method according to claim 8, wherein the duration of said mechanical grinding process is 1 to 200 hours.
11. A method of manufacturing an electrode at least for use as a secondary element, said electrode having a surface of Ti, V, Cr, Mn, Fe or Nb, said method comprising the step of exposing said surface to oxygen to form with the elements of said electrode material, in situ, a metal oxide at least on the surface of said electrode thereby providing for a catalyst facilitating the hydrogenation and dehydrogenation of said electrode material.
12. A method according to claim 13, wherein the surface of said electrode material is chemically activated before being exposed to said oxygen for forming said oxide.
13. A method according to claim 13, wherein the surface of said electrode material is mechanically activated before it is exposed to said oxygen to form the oxide.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19913714A DE19913714A1 (en) | 1999-03-26 | 1999-03-26 | Metal-containing material and process for its manufacture |
| DE19915142A DE19915142B4 (en) | 1999-03-26 | 1999-03-26 | Metal-containing electrode material for primary and secondary elements |
| DE19913714.5 | 1999-03-26 | ||
| DE19915142.3 | 1999-03-26 | ||
| PCT/DE1999/002974 WO2000058206A1 (en) | 1999-03-26 | 1999-09-17 | Metalliferous storage material for hydrogen and method for producing same |
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| Publication Number | Publication Date |
|---|---|
| CA2368437A1 CA2368437A1 (en) | 2000-10-05 |
| CA2368437C true CA2368437C (en) | 2008-02-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002368437A Expired - Fee Related CA2368437C (en) | 1999-03-26 | 1999-09-17 | Metalliferous storage material for hydrogen and method for producing same |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6752881B2 (en) |
| EP (1) | EP1169263B1 (en) |
| JP (1) | JP4121711B2 (en) |
| AT (1) | ATE310711T1 (en) |
| CA (1) | CA2368437C (en) |
| DE (1) | DE59912841D1 (en) |
| WO (1) | WO2000058206A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19915142B4 (en) * | 1999-03-26 | 2006-05-04 | Gkss-Forschungszentrum Geesthacht Gmbh | Metal-containing electrode material for primary and secondary elements |
| CA2389939A1 (en) * | 2002-06-25 | 2003-12-25 | Alicja Zaluska | New type of catalytic materials based on active metal-hydrogen-electronegative element complexes for reactions involving hydrogen transfer |
| DE10337970B4 (en) * | 2003-08-19 | 2009-04-23 | Gkss-Forschungszentrum Geesthacht Gmbh | Metal-containing, hydrogen storage material and process for its preparation |
| DE102004002120A1 (en) * | 2004-01-14 | 2005-08-18 | Gkss-Forschungszentrum Geesthacht Gmbh | Metal-containing, hydrogen storage material and process for its preparation |
| JP2007330877A (en) * | 2006-06-14 | 2007-12-27 | Taiheiyo Cement Corp | Hydrogen storage material and method for producing the same |
| KR100811116B1 (en) * | 2006-11-14 | 2008-03-06 | 한국과학기술연구원 | Method of manufacturing magnesium-based hydrogen storage material |
| JP2008266781A (en) * | 2007-03-24 | 2008-11-06 | Tokai Univ | Method for producing Mg-Al-based hydrogen storage alloy powder, and Mg-Al-based hydrogen storage alloy powder obtained by the production method |
| DE102008063895B3 (en) * | 2008-12-19 | 2010-06-10 | Gkss-Forschungszentrum Geesthacht Gmbh | Method for activation or regeneration of a hydrogen storage material |
| US20130004413A1 (en) * | 2011-06-29 | 2013-01-03 | GM Global Technology Operations LLC | Oxides-based material, device, and process for hydrogen storage |
| KR102041127B1 (en) * | 2018-03-27 | 2019-11-27 | 한밭대학교 산학협력단 | Synthetic method of single phase oxide for hydrogen storage with TiO2 crystal phase and single phase oxide for hydrogen storage using the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61143544A (en) * | 1984-12-04 | 1986-07-01 | Suzuki Shiyoukan:Kk | Material for reversibly occluding and releasing hydrogen |
| DE3535378A1 (en) * | 1985-10-03 | 1987-04-16 | Max Planck Gesellschaft | POWDERED HYDROGEN STORAGE MATERIAL AND ITS PRODUCTION |
| JPH03281710A (en) * | 1990-03-29 | 1991-12-12 | Mitsui Mining & Smelting Co Ltd | Manufacture of alloy powder |
| US5616432A (en) * | 1994-06-14 | 1997-04-01 | Ovonic Battery Company, Inc. | Electrochemical hydrogen storage alloys and batteries fabricated from Mg containing base alloys |
| KR19980033322A (en) * | 1996-10-31 | 1998-07-25 | 가나가와지히로 | Hydrogen Scavenging Alloy Containing Composition and Electrode Using the Same |
| US5864072A (en) * | 1997-01-09 | 1999-01-26 | Shin-Etsu Chemical Co., Ltd. | Hydrogen storage alloy and method for producing the same |
-
1999
- 1999-09-17 JP JP2000607919A patent/JP4121711B2/en not_active Expired - Fee Related
- 1999-09-17 AT AT99955727T patent/ATE310711T1/en not_active IP Right Cessation
- 1999-09-17 DE DE59912841T patent/DE59912841D1/en not_active Expired - Lifetime
- 1999-09-17 CA CA002368437A patent/CA2368437C/en not_active Expired - Fee Related
- 1999-09-17 EP EP99955727A patent/EP1169263B1/en not_active Expired - Lifetime
- 1999-09-17 WO PCT/DE1999/002974 patent/WO2000058206A1/en not_active Ceased
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- 2001-09-25 US US09/962,859 patent/US6752881B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CA2368437A1 (en) | 2000-10-05 |
| EP1169263A1 (en) | 2002-01-09 |
| EP1169263B1 (en) | 2005-11-23 |
| ATE310711T1 (en) | 2005-12-15 |
| JP2002540053A (en) | 2002-11-26 |
| WO2000058206A1 (en) | 2000-10-05 |
| US20020061814A1 (en) | 2002-05-23 |
| JP4121711B2 (en) | 2008-07-23 |
| US6752881B2 (en) | 2004-06-22 |
| DE59912841D1 (en) | 2005-12-29 |
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