CA2316289C - Process for manufacturing nanocrystalline metal hydrides - Google Patents
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- CA2316289C CA2316289C CA002316289A CA2316289A CA2316289C CA 2316289 C CA2316289 C CA 2316289C CA 002316289 A CA002316289 A CA 002316289A CA 2316289 A CA2316289 A CA 2316289A CA 2316289 C CA2316289 C CA 2316289C
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- C—CHEMISTRY; METALLURGY
- 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
- C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
- C01B6/243—Hydrides containing at least two metals; Addition complexes thereof containing only hydrogen, aluminium and alkali metals, e.g. Li(AlH4)
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- C—CHEMISTRY; METALLURGY
- 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
- C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
Abstract
In a process for preparing nanocrystalline metal hydrides, an elementary metal hydride of a first type is subjected with at least one elementary metal or at least another metal hydride to a mechanical grinding process in order to produce an alloyed hydride.
Description
PROCESS FOR MANUFACTURING NANOCRYSTALLINE METAL HYDRIDES
DESCRIPTION
The invention concerns a process for manufacturing nano-crystalline metal hydrides.
It is known that hydrogen storage devices, known as hy-dride storage devices, can be formed on the basis of reversible metal hydrides. This involves charging the storage device un-der release of heat, wherein hydrogen is bonded by chemisorp-tion and is discharged again by the application of heat. Thus hydrogen storage devices could form outstandingly good energy storage devices for mobile and/or stationary applications, i.e.
they should provide in the future considerable storage poten-tial because no harmful emissions are generated during the dis-charge of the hydrogen storage device.
What are known as nanocrystalline hydrides are very suit-able for this kind of hydride storage devices. These hydrides are characterized by rapid hydrogen assimilation and release kinetics. However, until now, their manufacture has been very complicated and expensive. Up to now, nanocrystalline alloys were manufactured firstly by high-energy grinding from elemen-tal components or pre-alloys, with the grinding durations some-times being very long. In a subsequent process step, these na-nocrystalline alloys were subjected, where required, to a multi-stage heat treatment under a high hydrogen pressure to be hydrogenated in this manner. Furthermore, for many alloys, multiple charging and discharging with hydrogen is necessary in order to achieve full storage capacity.
Alternatively, attempts have been made to synthesize the corresponding hydrides by grinding in an atmosphere of hydrogen or by purely chemical means. However, it was observed that the yield of the desired hydrides is smaller and additional un-wanted phases may sometimes appear.
Furthermore, certain phases are not even obtainable with these conventional methods.
Thus, it is the object of the present invention to provide a process of the kind initially mentioned, with which however the manufacture of stable and metastable hydrides or hydrides of metastable alloys can be achieved, namely, with a very high yield of up to 100%. The process should further be capable of being carried out under comparatively simply manageable condi-tions and should require a comparatively small input of energy.
The object is solved according to the invention by sub-jecting an elemental metal hydride of a first kind to a me-chanical grinding process with at least one elemental metal or at least one additional metal hydride to create an alloy hy-dride.
The advantage of the process according to the invention lies essentially in the fact that, as intended, the manufacture of stable and metastable hydrides or hydrides of metastable al-loys is possible in a comparatively simple way with a high yield of up at 100%, and the disadvantages that occur in the processes known in the state of the art for manufacturing hy-dride storage devices are avoided. In addition, the process according to the invention, permits the manufacture of hydrides that could not be manufactured at all using known processes.
DESCRIPTION
The invention concerns a process for manufacturing nano-crystalline metal hydrides.
It is known that hydrogen storage devices, known as hy-dride storage devices, can be formed on the basis of reversible metal hydrides. This involves charging the storage device un-der release of heat, wherein hydrogen is bonded by chemisorp-tion and is discharged again by the application of heat. Thus hydrogen storage devices could form outstandingly good energy storage devices for mobile and/or stationary applications, i.e.
they should provide in the future considerable storage poten-tial because no harmful emissions are generated during the dis-charge of the hydrogen storage device.
What are known as nanocrystalline hydrides are very suit-able for this kind of hydride storage devices. These hydrides are characterized by rapid hydrogen assimilation and release kinetics. However, until now, their manufacture has been very complicated and expensive. Up to now, nanocrystalline alloys were manufactured firstly by high-energy grinding from elemen-tal components or pre-alloys, with the grinding durations some-times being very long. In a subsequent process step, these na-nocrystalline alloys were subjected, where required, to a multi-stage heat treatment under a high hydrogen pressure to be hydrogenated in this manner. Furthermore, for many alloys, multiple charging and discharging with hydrogen is necessary in order to achieve full storage capacity.
Alternatively, attempts have been made to synthesize the corresponding hydrides by grinding in an atmosphere of hydrogen or by purely chemical means. However, it was observed that the yield of the desired hydrides is smaller and additional un-wanted phases may sometimes appear.
Furthermore, certain phases are not even obtainable with these conventional methods.
Thus, it is the object of the present invention to provide a process of the kind initially mentioned, with which however the manufacture of stable and metastable hydrides or hydrides of metastable alloys can be achieved, namely, with a very high yield of up to 100%. The process should further be capable of being carried out under comparatively simply manageable condi-tions and should require a comparatively small input of energy.
The object is solved according to the invention by sub-jecting an elemental metal hydride of a first kind to a me-chanical grinding process with at least one elemental metal or at least one additional metal hydride to create an alloy hy-dride.
The advantage of the process according to the invention lies essentially in the fact that, as intended, the manufacture of stable and metastable hydrides or hydrides of metastable al-loys is possible in a comparatively simple way with a high yield of up at 100%, and the disadvantages that occur in the processes known in the state of the art for manufacturing hy-dride storage devices are avoided. In addition, the process according to the invention, permits the manufacture of hydrides that could not be manufactured at all using known processes.
Depending on the hydrides used to manufacture nanocrystal-line metal hydrides, the grinding process for the mixture of elemental metal hydride, metal or several additional metal hy-drides is preferably carried out for a predetermined period, preferably in the range from 20 to 200 hours.
In principle, however the grinding procedure period is de-pendent on the design of the grinding equipment used, so that the specified and preferred grinding times may not be reached or may be exceeded. However, in general, it can be said that the grinding times according to the invention are significantly shorter than those employed during grinding without the use of hydrides.
Grinding under an inert gas atmosphere has been found to be advantageous. As already mentioned above, hydrides, for ex-ample magnesium-iron hydrides, were hitherto manufactured by annealing at high temperature under a high pressure of hydro-gen. Remaining with this example, attempts were made to grind magnesium and iron in a hydrogen atmosphere, but this did not lead to the synthesis of the desired magnesium-iron hydride.
However, according to the invention, it is possible, by grind-ing magnesium hydride and iron in a particular molar ratio un-der an inert gas atmosphere, to synthesize a hydrogen-enriched hydride directly at the end of the grinding process, which has proved very successful specially when using argon as the inert gas.
Especially good results were achieved with the process, when the first elemental metal hydride consisted of metals of the Ist or II d main group of the periodic system. The metals are preferably Li, Na, K, Mg, Ca, Sc, Y, Ti, V, Nb, or La, with the elements preferably being Fe, Co, Nb, Cu, Zn, Al, and Si.
Especially good process results were also achieved when pref-erably the elemental metal consisted of elements of the VIIIth sub-group of the periodic system of elements.
Preferably, the second metal hydride consists of a mixture of elements of the Ist and IIIrd main group of the periodic sys-tem of elements. Carrying out the process in such a way pro-vides for very good results in the desired sense.
Basically, the process can also be carried out if the metal hydrides and/or the metal are not present in the form of powder at the start of the grinding procedure. It is espe-cially advantageous to first convert the metal hydride and/or the metal into powder form and then to subject the powdered metal hydride and/or the metal to the grinding process accord-ing to the invention because the process can then be operated efficiently and consequently with an extremely high yield.
The invention will now be described in detail on the basis of several examples with reference to the following diagram-matic illustrations. It is shown in:
Fig. 1 the x-ray diffraction pattern of the Mg2FeH6 pow-der, Fig. 2 confirmation of the results of Example 1 by an examination using a differential scanning calorimeter, DSC, un-der hydrogen.
Fig. 3 the x-ray diffraction pattern of the Na3A1H6 pow-der, Fig. 4 confirmation of the results of Fig. 3 by an ex-amination using a differential scanning calorimeter, DSC, under hydrogen, Fig. 5 the x-ray diffraction pattern of the Na2AlLiH6 powder, Fig. 6 the x-ray diffraction pattern of the (MgH2)67Ni33 powder mixture after different grinding periods, Fig. 7 - the x-ray diffraction pattern of the MgzNiH4/MgH2 powder mixture after different grinding periods, Fig. 8 - the PCT diagram of the Mg2NiHq/MgH2 two-phase com-posite powder, Fig. 9 - the x-ray diffraction pattern of the (Mg-10 mol%
MgH2)67Ni33 powder mixture with different grinding periods, and Fig. 10 - a comparison of the hydrogen absorption kinetics at 300 C for Mg2Ni, calculated with different values of MgH2.
It is known that magnesium and iron are not miscible. The usual way of manufacturing hydrides employed for example heat treatment of the constituents, which was to provide the desired hydride. This step was performed at very high temperature and under a high pressure of hydrogen. Earlier experiments basi-cally showed that the grinding of magnesium and iron under an atmosphere of hydrogen however did not lead to a synthesis of, for example, a hydride in the form of Mg2FeH6. But these ex-periments had shown that grinding the constituents basically made a reduction of the heat treatment temperature and of the hydrogen pressure possible.
In the process of the invention, elemental hydrides and elemental metal of the elements of the VIII"' sub-group of the periodic system of the elements, for example, MgH2 and Fe, are ground under an argon atmosphere. According to the invention, it has been found that, at the end of the grinding procedure, it is possible to synthesize the resulting hydride MgZFeH6 di-rectly without subsequent annealing.
Example 1:
SYNTHESIS OF Mg2FeHb Experimental details: 3 g of Mg of MgH2 and Fe in a molar ratio of 2:1 were put into a 60 ml cup together with 3 steel balls (two of 1.27 cm and one of 1.429 cm diameter) . The pow-der was subjected to intense mechanical pulverizing in a high-energy ball-milling machine of the type SPEX 8000 (SPEX is a registered trademark) . The grinding was carried out for 60 hours'under an argon atmosphere. The x-ray diffraction pattern shown in Fig. 1 of the resulting Mg2FeH6 powder shows the hy-dride synthesized according to example 1. The result was con-firmed by an examination using a differential scanning calo-rimeter, DSC, under hydrogen. The x-ray diffraction pattern of the powder according to example 1 shows for the MgzFeH6 a crys-tal size of 22 nm.
Example 2:
SYNTHESIS OF Na.3AlH6 Experimental details: 3 g of NaH and NaAlH4 in a molar ra-tio of 2 were put into a 60 ml cup together with 3 steel balls (two of 1.27 cm and one of 1.429 cm diameter) . The powder was subjected to intense mechanical pulverizing in a high-energy grinding machine of the type SPEX 8000. The grinding was car-ried out for 20 hours under an argon atmosphere. The x-ray diffraction pattern of the powder illustrated in Fig. 3 shows the formation of Na3AlH6 according to Example 2. This result was confirmed by verification using a differential scanning calorimeter, DSC, under hydrogen, cf. Fig. 4.
Example 3:
SYNTHESIS OF Na2AlLiH6 Experimental details: 3g of NaH, LiH and NaAlH9 in a molar ratio of 1:1:1 were placed into a 60 ml cup together with 3 steel balls (two of 1.27 cm and one of 1.429 cm diameter). The powder was subjected to intense mechanical grinding in a high-energy ball-milling machine of the type SPEX 8000. The grind-ing was carried out under an argon atmosphere for a period of 40 hours. The X-ray diffraction pattern of the powder illus-trated in Fig. 5 shows the formation of the Na2AlLiH6 hydride.
Example 4:
SYNTHESIS OF Mg2NiH4 Experimental details: MgH2 powder and elemental Ni powder were mixed in a molar ratio of 2:1. 40 g of this powder mix-ture was ground in a planetary ball mill (type Fritsch P5TM) at 230 rpm, using a hardened chrome steel cup (with a volume of 250 ml) and balls (with a diameter of 10 mm). A ball to powder weight ratio of 10:1 was chosen. The grinding experiments were carried out in a argon atmosphere for up to 200 hours.
Fig. 6 shows the X-ray diffraction pattern of the powder obtained after different grinding periods. The Bragg reflec-tions of the starting material decrease continuously as the grinding period increases, which is illustrated by the dashed line. The formation of the Mg2NiH9 hydride phase is already recognizable after grinding for 20 hours. The reaction is com-plete after 50 hours, and the structure of the hydride obtained remains unchanged even after further grinding.
Example 5:
Synthesis of a Mg2NiH9/MgH2 (Mg83Ni17) mixture using MgH2 Experimental details: MgH2 powder and elemental Ni powder were mixed in a molar ratio 5:1. 40g of this powder mixture was ground in a planetary ball mill (type Fritsch P5T"') at 230 rpm, using a hardened chrome steel vial (with a volume of 250 ml) and balls (with a diameter of 10mm) . A ball to powder weight ratio of 10:1 was chosen. The grinding experiments were carried out in an argon atmosphere for up to 200 hours.
Fig. 7 shows the X-ray diffraction pattern of the powder after different grinding durations. The Bragg reflections of the starting materials decrease with increasing grinding dura-tion. After 100 hours of grinding, the Ni peaks have disap-peared and the MgzNiH9 hydride has been formed. In this way an Mg2NiH9/MgH2 two-phase hydride has been formed. The structure of the two-phase composite hydride remains unaltered even after further grinding.
Fig.8 shows the PCT (Pressure-Concentration-Temperature) diagram of the composite. The two-pressure plateux, which re-lates to the formation of Mg2NiH9 and MgH2, can be clearly dis-tinguished and/or kept separate. The total hydrogen capacity of the hydride is 5% wt./wt.
Example 6:
Synthesis of Mg2NiHo,3/Mg2Ni hydride using 10 mol % MgH2 and 90 mol % Mg Experimental details: Mg powder and MgH2 are mixed in a molar ratio of 9:1. Thereafter this mixture is mixed with ele-mental Ni powder in a molar ratio of 2:1. 40g of the powder mixture are ground in a planetary ball mill (type Fritsch P5TM) at 230 rpm, using a hardened chrome steel vial (with a volume of 250 ml) and balls (with a diameter of 10 mm) . A ball to powder weight ratio of 10:1 was chosen. The grinding experi-ments were carried out in an argon atmosphere for up to 200 hours.
Fig. 9 shows an x-ray diffraction pattern of the hydride for different grinding times. The Bragg reflections of the MgH2 have almost disappeared after only 5 hours of grinding.
After a grinding time of 20 hours, the Ni peaks have also sig-nificantly decreased and new phases have formed. Finally, Ni diffraction peaks are no longer visible after 200 hours of grinding and an Mg2NiHo.3/Mg2Ni two-phase hydride is obtained.
The kinetic properties of the material described in Exam-ples 4 and 6 during the first absorption cycle (after the ini-tial desorption) are compared with the properties of Mg2Ni manufactured from the pure materials, cf. Fig. 10. Whilst the Mg2NiHo,3/Mg2Ni two-phase mixture represents merely a minimal im-provement with regard to the material that had been ground without MgH2, the MgZNiH9, that was ground with 100% MgH2 is clearly the better one, and achieves up to 80% of the total hy-drogen absorption capacity within 20 seconds.
In principle, however the grinding procedure period is de-pendent on the design of the grinding equipment used, so that the specified and preferred grinding times may not be reached or may be exceeded. However, in general, it can be said that the grinding times according to the invention are significantly shorter than those employed during grinding without the use of hydrides.
Grinding under an inert gas atmosphere has been found to be advantageous. As already mentioned above, hydrides, for ex-ample magnesium-iron hydrides, were hitherto manufactured by annealing at high temperature under a high pressure of hydro-gen. Remaining with this example, attempts were made to grind magnesium and iron in a hydrogen atmosphere, but this did not lead to the synthesis of the desired magnesium-iron hydride.
However, according to the invention, it is possible, by grind-ing magnesium hydride and iron in a particular molar ratio un-der an inert gas atmosphere, to synthesize a hydrogen-enriched hydride directly at the end of the grinding process, which has proved very successful specially when using argon as the inert gas.
Especially good results were achieved with the process, when the first elemental metal hydride consisted of metals of the Ist or II d main group of the periodic system. The metals are preferably Li, Na, K, Mg, Ca, Sc, Y, Ti, V, Nb, or La, with the elements preferably being Fe, Co, Nb, Cu, Zn, Al, and Si.
Especially good process results were also achieved when pref-erably the elemental metal consisted of elements of the VIIIth sub-group of the periodic system of elements.
Preferably, the second metal hydride consists of a mixture of elements of the Ist and IIIrd main group of the periodic sys-tem of elements. Carrying out the process in such a way pro-vides for very good results in the desired sense.
Basically, the process can also be carried out if the metal hydrides and/or the metal are not present in the form of powder at the start of the grinding procedure. It is espe-cially advantageous to first convert the metal hydride and/or the metal into powder form and then to subject the powdered metal hydride and/or the metal to the grinding process accord-ing to the invention because the process can then be operated efficiently and consequently with an extremely high yield.
The invention will now be described in detail on the basis of several examples with reference to the following diagram-matic illustrations. It is shown in:
Fig. 1 the x-ray diffraction pattern of the Mg2FeH6 pow-der, Fig. 2 confirmation of the results of Example 1 by an examination using a differential scanning calorimeter, DSC, un-der hydrogen.
Fig. 3 the x-ray diffraction pattern of the Na3A1H6 pow-der, Fig. 4 confirmation of the results of Fig. 3 by an ex-amination using a differential scanning calorimeter, DSC, under hydrogen, Fig. 5 the x-ray diffraction pattern of the Na2AlLiH6 powder, Fig. 6 the x-ray diffraction pattern of the (MgH2)67Ni33 powder mixture after different grinding periods, Fig. 7 - the x-ray diffraction pattern of the MgzNiH4/MgH2 powder mixture after different grinding periods, Fig. 8 - the PCT diagram of the Mg2NiHq/MgH2 two-phase com-posite powder, Fig. 9 - the x-ray diffraction pattern of the (Mg-10 mol%
MgH2)67Ni33 powder mixture with different grinding periods, and Fig. 10 - a comparison of the hydrogen absorption kinetics at 300 C for Mg2Ni, calculated with different values of MgH2.
It is known that magnesium and iron are not miscible. The usual way of manufacturing hydrides employed for example heat treatment of the constituents, which was to provide the desired hydride. This step was performed at very high temperature and under a high pressure of hydrogen. Earlier experiments basi-cally showed that the grinding of magnesium and iron under an atmosphere of hydrogen however did not lead to a synthesis of, for example, a hydride in the form of Mg2FeH6. But these ex-periments had shown that grinding the constituents basically made a reduction of the heat treatment temperature and of the hydrogen pressure possible.
In the process of the invention, elemental hydrides and elemental metal of the elements of the VIII"' sub-group of the periodic system of the elements, for example, MgH2 and Fe, are ground under an argon atmosphere. According to the invention, it has been found that, at the end of the grinding procedure, it is possible to synthesize the resulting hydride MgZFeH6 di-rectly without subsequent annealing.
Example 1:
SYNTHESIS OF Mg2FeHb Experimental details: 3 g of Mg of MgH2 and Fe in a molar ratio of 2:1 were put into a 60 ml cup together with 3 steel balls (two of 1.27 cm and one of 1.429 cm diameter) . The pow-der was subjected to intense mechanical pulverizing in a high-energy ball-milling machine of the type SPEX 8000 (SPEX is a registered trademark) . The grinding was carried out for 60 hours'under an argon atmosphere. The x-ray diffraction pattern shown in Fig. 1 of the resulting Mg2FeH6 powder shows the hy-dride synthesized according to example 1. The result was con-firmed by an examination using a differential scanning calo-rimeter, DSC, under hydrogen. The x-ray diffraction pattern of the powder according to example 1 shows for the MgzFeH6 a crys-tal size of 22 nm.
Example 2:
SYNTHESIS OF Na.3AlH6 Experimental details: 3 g of NaH and NaAlH4 in a molar ra-tio of 2 were put into a 60 ml cup together with 3 steel balls (two of 1.27 cm and one of 1.429 cm diameter) . The powder was subjected to intense mechanical pulverizing in a high-energy grinding machine of the type SPEX 8000. The grinding was car-ried out for 20 hours under an argon atmosphere. The x-ray diffraction pattern of the powder illustrated in Fig. 3 shows the formation of Na3AlH6 according to Example 2. This result was confirmed by verification using a differential scanning calorimeter, DSC, under hydrogen, cf. Fig. 4.
Example 3:
SYNTHESIS OF Na2AlLiH6 Experimental details: 3g of NaH, LiH and NaAlH9 in a molar ratio of 1:1:1 were placed into a 60 ml cup together with 3 steel balls (two of 1.27 cm and one of 1.429 cm diameter). The powder was subjected to intense mechanical grinding in a high-energy ball-milling machine of the type SPEX 8000. The grind-ing was carried out under an argon atmosphere for a period of 40 hours. The X-ray diffraction pattern of the powder illus-trated in Fig. 5 shows the formation of the Na2AlLiH6 hydride.
Example 4:
SYNTHESIS OF Mg2NiH4 Experimental details: MgH2 powder and elemental Ni powder were mixed in a molar ratio of 2:1. 40 g of this powder mix-ture was ground in a planetary ball mill (type Fritsch P5TM) at 230 rpm, using a hardened chrome steel cup (with a volume of 250 ml) and balls (with a diameter of 10 mm). A ball to powder weight ratio of 10:1 was chosen. The grinding experiments were carried out in a argon atmosphere for up to 200 hours.
Fig. 6 shows the X-ray diffraction pattern of the powder obtained after different grinding periods. The Bragg reflec-tions of the starting material decrease continuously as the grinding period increases, which is illustrated by the dashed line. The formation of the Mg2NiH9 hydride phase is already recognizable after grinding for 20 hours. The reaction is com-plete after 50 hours, and the structure of the hydride obtained remains unchanged even after further grinding.
Example 5:
Synthesis of a Mg2NiH9/MgH2 (Mg83Ni17) mixture using MgH2 Experimental details: MgH2 powder and elemental Ni powder were mixed in a molar ratio 5:1. 40g of this powder mixture was ground in a planetary ball mill (type Fritsch P5T"') at 230 rpm, using a hardened chrome steel vial (with a volume of 250 ml) and balls (with a diameter of 10mm) . A ball to powder weight ratio of 10:1 was chosen. The grinding experiments were carried out in an argon atmosphere for up to 200 hours.
Fig. 7 shows the X-ray diffraction pattern of the powder after different grinding durations. The Bragg reflections of the starting materials decrease with increasing grinding dura-tion. After 100 hours of grinding, the Ni peaks have disap-peared and the MgzNiH9 hydride has been formed. In this way an Mg2NiH9/MgH2 two-phase hydride has been formed. The structure of the two-phase composite hydride remains unaltered even after further grinding.
Fig.8 shows the PCT (Pressure-Concentration-Temperature) diagram of the composite. The two-pressure plateux, which re-lates to the formation of Mg2NiH9 and MgH2, can be clearly dis-tinguished and/or kept separate. The total hydrogen capacity of the hydride is 5% wt./wt.
Example 6:
Synthesis of Mg2NiHo,3/Mg2Ni hydride using 10 mol % MgH2 and 90 mol % Mg Experimental details: Mg powder and MgH2 are mixed in a molar ratio of 9:1. Thereafter this mixture is mixed with ele-mental Ni powder in a molar ratio of 2:1. 40g of the powder mixture are ground in a planetary ball mill (type Fritsch P5TM) at 230 rpm, using a hardened chrome steel vial (with a volume of 250 ml) and balls (with a diameter of 10 mm) . A ball to powder weight ratio of 10:1 was chosen. The grinding experi-ments were carried out in an argon atmosphere for up to 200 hours.
Fig. 9 shows an x-ray diffraction pattern of the hydride for different grinding times. The Bragg reflections of the MgH2 have almost disappeared after only 5 hours of grinding.
After a grinding time of 20 hours, the Ni peaks have also sig-nificantly decreased and new phases have formed. Finally, Ni diffraction peaks are no longer visible after 200 hours of grinding and an Mg2NiHo.3/Mg2Ni two-phase hydride is obtained.
The kinetic properties of the material described in Exam-ples 4 and 6 during the first absorption cycle (after the ini-tial desorption) are compared with the properties of Mg2Ni manufactured from the pure materials, cf. Fig. 10. Whilst the Mg2NiHo,3/Mg2Ni two-phase mixture represents merely a minimal im-provement with regard to the material that had been ground without MgH2, the MgZNiH9, that was ground with 100% MgH2 is clearly the better one, and achieves up to 80% of the total hy-drogen absorption capacity within 20 seconds.
Claims (6)
1. A process for manufacturing nanocrystalline metal hydrides, comprising the step of subjecting a metal hydride to a mechanical milling process with at least one metal to produce an alloy hydride, wherein the milling process takes place in an inert gas atmosphere.
2. The process according to claim 1, wherein the milling process is carried out for a pre-determined period of time of up to 200 hours.
3. The process according to claim 1, wherein the inert gas is argon.
4. The process according to claim 1 wherein the metal hydride is selected from the group consisting of hydrides of Li, Na, K, Mg, Ca, Sc, Y, Ti, Zr, V, Nb and La.
5. The process according to claim 1, wherein the metal consists of at least one selected from the group consisting of Fe, Co, Ni, Cu, Zn, Al and Si.
6. The process according to claim 1 wherein the metal hydride and the metal are supplied to the milling process in the form of powder.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19758384.9 | 1997-12-23 | ||
| DE19758384A DE19758384C2 (en) | 1997-12-23 | 1997-12-23 | Process for the production of nanocrystalline metal hydrides |
| PCT/DE1998/003765 WO1999033747A1 (en) | 1997-12-23 | 1998-12-22 | Process for preparing nanocrystalline metal hydrides |
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| Publication Number | Publication Date |
|---|---|
| CA2316289A1 CA2316289A1 (en) | 1999-07-08 |
| CA2316289C true CA2316289C (en) | 2009-10-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002316289A Expired - Fee Related CA2316289C (en) | 1997-12-23 | 1998-12-22 | Process for manufacturing nanocrystalline metal hydrides |
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|---|---|
| US (1) | US6387152B1 (en) |
| EP (1) | EP1042218B1 (en) |
| JP (1) | JP3824052B2 (en) |
| AT (1) | ATE548325T1 (en) |
| CA (1) | CA2316289C (en) |
| DE (1) | DE19758384C2 (en) |
| WO (1) | WO1999033747A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19758384C2 (en) * | 1997-12-23 | 2002-08-01 | Geesthacht Gkss Forschung | Process for the production of nanocrystalline metal hydrides |
| EP1174385B1 (en) | 2000-05-31 | 2004-10-06 | Honda Giken Kogyo Kabushiki Kaisha | Process for producing hydrogen absorbing alloy powder, hydrogen absorbing alloy powder, and hydrogen-storing tank for mounting in vehicle |
| US20070092437A1 (en) * | 2001-12-11 | 2007-04-26 | Young-Kyun Kwon | Increasing hydrogen adsorption of nanostructured storage materials by modifying sp2 covalent bonds |
| US7169489B2 (en) * | 2002-03-15 | 2007-01-30 | Fuelsell Technologies, Inc. | Hydrogen storage, distribution, and recovery system |
| 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 |
| US20040065171A1 (en) * | 2002-10-02 | 2004-04-08 | Hearley Andrew K. | Soild-state hydrogen storage systems |
| EP1558520B1 (en) * | 2002-11-01 | 2011-01-26 | Savannah River Nuclear Solutions, LLC | Complex hydrides for hydrogen storage |
| US6939449B2 (en) * | 2002-12-24 | 2005-09-06 | General Atomics | Water electrolyzer and system |
| US7140567B1 (en) * | 2003-03-11 | 2006-11-28 | Primet Precision Materials, Inc. | Multi-carbide material manufacture and use as grinding media |
| US7578457B2 (en) * | 2003-03-11 | 2009-08-25 | Primet Precision Materials, Inc. | Method for producing fine dehydrided metal particles using grinding media |
| US7029649B2 (en) * | 2003-08-26 | 2006-04-18 | General Motors Corporation | Combinations of hydrogen storage materials including amide/imide |
| DE102004053865A1 (en) * | 2004-11-04 | 2006-05-24 | Gkss-Forschungszentrum Geesthacht Gmbh | Method for producing metal components |
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| US9234264B2 (en) * | 2004-12-07 | 2016-01-12 | Hydrexia Pty Limited | Magnesium alloys for hydrogen storage |
| DE102004061286B4 (en) * | 2004-12-14 | 2021-09-16 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Hydrogen-storing composite material as well as a device for the reversible storage of hydrogen |
| WO2006104079A1 (en) * | 2005-03-28 | 2006-10-05 | Taiheiyo Cement Corporation | Hydrogen-storing materials and process for production of the same |
| US20070098803A1 (en) * | 2005-10-27 | 2007-05-03 | Primet Precision Materials, Inc. | Small particle compositions and associated methods |
| NO327822B1 (en) * | 2006-05-16 | 2009-10-05 | Inst Energiteknik | Process for the preparation of AlH3 and structurally related phases, and use of such material |
| ITMI20071962A1 (en) * | 2007-10-11 | 2009-04-12 | Comision Nac De En Atomic A | COMPOSITE MATERIAL FOR STORAGE OF HYDROGEN WITH VERY HIGH ABSORPTION AND DESORPTION SPEED AND PROCEDURE FOR THE PRODUCTION OF THAT MATERIAL |
| CN102782390B (en) | 2010-02-24 | 2015-05-13 | 海德瑞克斯亚股份有限公司 | Hydrogen release system, system for hydrogen supply delivery and method for supply hydrogen |
| KR101378307B1 (en) * | 2012-01-27 | 2014-03-27 | 한국교통대학교산학협력단 | Manufacturing method of vanadium-aluminum composites for hydrogen production membrane and composites by the method |
| CN104445070A (en) * | 2014-12-02 | 2015-03-25 | 安徽工业大学 | Preparation method of magnesium-based bimetallic hydride containing nickel and rare earth metal hydride nanoparticles |
| US11141784B2 (en) | 2015-07-23 | 2021-10-12 | Hydrexia Pty Ltd. | Mg-based alloy for hydrogen storage |
| CN111252733A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Preparation method of multi-element metal hydride |
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| CA654035A (en) * | 1962-12-11 | Clasen Hermann | Process for the production of soluble compounds | |
| DE1216260B (en) * | 1960-10-19 | 1966-05-12 | Metallgesellschaft Ag | Process for the production of double hydrides of lithium |
| DE6950029U (en) * | 1969-12-27 | 1970-06-25 | Spohn Karl | ALARM CLOCK. |
| DE3247360A1 (en) * | 1982-12-22 | 1984-07-05 | Studiengesellschaft Kohle mbH, 4330 Mülheim | METHOD FOR PRODUCING ACTIVE MAGNETIC SIUMHDRID MAGNESIUM HYDROGEN STORAGE SYSTEMS |
| DE3813224A1 (en) * | 1988-04-20 | 1988-08-25 | Krupp Gmbh | METHOD FOR ADJUSTING FINE CRYSTALLINE TO NANOCRISTALLINE STRUCTURES IN METAL-METAL METALOID POWDER |
| CA2117158C (en) * | 1994-03-07 | 1999-02-16 | Robert Schulz | Nickel-based nanocristalline alloys and their use for the transport and storing of hydrogen |
| EP0815273B1 (en) * | 1995-02-02 | 2001-05-23 | Hydro-Quebec | NANOCRYSTALLINE Mg-BASED MATERIALS AND USE THEREOF FOR THE TRANSPORTATION AND STORAGE OF HYDROGEN |
| DE59603454D1 (en) * | 1995-05-26 | 1999-12-02 | Goldschmidt Ag Th | Process for the production of X-ray amorphous and nanocrystalline metal powder |
| DE19526434A1 (en) * | 1995-07-19 | 1997-01-23 | Studiengesellschaft Kohle Mbh | Process for the reversible storage of hydrogen |
| US5906792A (en) * | 1996-01-19 | 1999-05-25 | Hydro-Quebec And Mcgill University | Nanocrystalline composite for hydrogen storage |
| US5837030A (en) * | 1996-11-20 | 1998-11-17 | Hydro-Quebec | Preparation of nanocrystalline alloys by mechanical alloying carried out at elevated temperatures |
| CA2218271A1 (en) * | 1997-10-10 | 1999-04-10 | Mcgill University | Method of fabrication of complex alkali mental hydrides |
| DE19758384C2 (en) * | 1997-12-23 | 2002-08-01 | Geesthacht Gkss Forschung | Process for the production of nanocrystalline metal hydrides |
| US6231636B1 (en) * | 1998-02-06 | 2001-05-15 | Idaho Research Foundation, Inc. | Mechanochemical processing for metals and metal alloys |
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| DE19758384A1 (en) | 1999-07-01 |
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| CA2316289A1 (en) | 1999-07-08 |
| JP2001527017A (en) | 2001-12-25 |
| WO1999033747A1 (en) | 1999-07-08 |
| EP1042218B1 (en) | 2012-03-07 |
| JP3824052B2 (en) | 2006-09-20 |
| US6387152B1 (en) | 2002-05-14 |
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