(19)
(11)EP 2 759 515 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
03.07.2019 Bulletin 2019/27

(21)Application number: 12848678.4

(22)Date of filing:  25.10.2012
(51)International Patent Classification (IPC): 
C01B 3/00(2006.01)
C22C 23/00(2006.01)
(86)International application number:
PCT/JP2012/077534
(87)International publication number:
WO 2013/069464 (16.05.2013 Gazette  2013/20)

(54)

METHOD FOR HYDROGEN OCCLUSION

VERFAHREN FÜR WASSERSTOFFEINSCHLUSS

PROCÉDÉ D'OCCLUSION D'HYDROGÈNE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 08.11.2011 JP 2011244373

(43)Date of publication of application:
30.07.2014 Bulletin 2014/31

(73)Proprietor: Kabushiki Kaisha Atsumitec
Shizuoka 433-8118 (JP)

(72)Inventors:
  • UCHIYAMA, Naoki
    Hamamatsu-shi Shizuoka 433-8118 (JP)
  • KANAI,Tomomi
    Hamamatsu-shi Shizuoka 433-8118 (JP)
  • HARADA, Kazumi
    Hamamatsu-shi Shizuoka 433-8118 (JP)

(74)Representative: MERH-IP Matias Erny Reichl Hoffmann Patentanwälte PartG mbB 
Paul-Heyse-Strasse 29
80336 München
80336 München (DE)


(56)References cited: : 
EP-A1- 1 176 219
JP-A- 2003 193 166
US-A- 5 199 972
JP-A- H11 343 524
JP-A- 2007 046 119
US-A1- 2012 100 065
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Technical Field



    [0001] The present invention relates to a hydrogen storage method using a hydrogen storage alloy, in particular, a hydrogen storage alloy in the form of a thin film.

    Background Art



    [0002] A hydrogen sensor is disclosed in Patent Document 1. An alloy used in this hydrogen sensor to store hydrogen is in the form of a thin film. The hydrogen sensor detects storage of hydrogen by making use of the property that the optical reflectivity of the alloy changes as the alloy stores hydrogen.

    [0003] Such an alloy capable of storing hydrogen can be used not only as a sensor but as an electrode of a hydrogen storage cell. Where the alloy is used as an electrode, it is desirable that the alloy should be able to store as much hydrogen as possible. However, hydrogen storage alloy has its own theoretical value represented by a ratio up to which hydrogen can be stored in the alloy, and it is not generally known that hydrogen storage alloy is capable of storing hydrogen in an amount exceeding its theoretical value.
    An MgNi alloy for storing hydrogen is for example known from US 5199972; To evaluate the hydrogen uptake in said document a cycling of dehydrogenation and hydrogenation is done. Further methods for investigation of hydrogen storage alloys are known from US 2012/0100065 A1 and EP 1176219 A1.

    Prior Art Document


    Patent Document



    [0004] Patent Document 1: Japanese Unexamined Patent Publication No. 2010-210242

    Summary of the Invention


    Problems to be solved by the Invention



    [0005] The present invention was created in view of the aforementioned conventional art, and an object thereof is to provide a hydrogen storage method whereby a hydrogen storage alloy can be made to store hydrogen up to its own maximum hydrogen storage amount exceeding a generally known theoretical value. In view of the hydrogen storage alloy known from-US 5199972 it is an object of the present invention to provide a method with which an excess amount of hydrogen can be stored in the alloy.

    Means for Solving the Problems



    [0006] To achieve the object, the present invention provides a hydrogen storage method including: a hydrogenation step of hydrogenating a hydrogen storage alloy of Mg2Ni or Mg6Ni while increasing pressure in an atmosphere; and a dehydrogenation step of dehydrogenating the hydrogenated hydrogen storage alloy while decreasing the pressure in the atmosphere, wherein in the hydrogenation step, a hydrogen storage ratio calculated as an atomic weight ratio between hydrogen and the hydrogen storage alloy is obtained beforehand as a theoretical value, a pressure at which the hydrogen storage alloy stores hydrogen up to the theoretical value is set as a first pressure value, a pressure value ten or more times greater than the first pressure value is set as a second pressure value, and the pressure in the atmosphere is increased up to the second pressure value; in the dehydrogenation step, the pressure in the atmosphere is decreased from the second pressure value to or below the first pressure value; and the hydrogenation step and the dehydrogenation step are repeatedly executed.

    [0007] The hydrogen storage alloy preferably has a particle sized in less than 10nm.

    Advantageous Effects of the Invention



    [0008] According to the present invention, hydrogen storage alloy can store hydrogen in excess of its theoretical value by repeatedly executing the hydrogenation step and the dehydrogenation step.

    [0009] Also, by using hydrogen storage alloy with a particle sized in less than 10nm, more particularly, a particle size of 5 nm or less, it is possible to lower the first pressure value, and since the second pressure value lowers correspondingly, it is unnecessary to apply a very high pressure for the storage of hydrogen.

    Brief Description of the Drawings



    [0010] FIG. 1 is a graph showing the relationship between hydrogen storage amount and pressure during execution of a hydrogen storage method according to the present invention.

    Mode for Carrying out the Invention



    [0011] FIG. 1 illustrates an exemplary case where Mg6Ni is used as a hydrogen storage alloy. Specifically, Mg6Ni was sputtered on both surfaces of each aramid film substrate with a size of 150 mm × 150 mm, to prepare four hydrogen storage alloy plates. The hydrogen storage alloy plates were exposed to a hydrogen atmosphere in an environment of 30°C and were repeatedly subjected to a hydrogenation step and a dehydrogenation step. The hydrogenation step is executed while increasing the pressure in the hydrogen atmosphere (in FIG. 1, indicated by solid lines). On the other hand, the dehydrogenation step is executed while decreasing the pressure in the hydrogen atmosphere (in FIG. 1, indicated by dotted lines).

    [0012] According to the present invention, a first pressure value and a second pressure value are set in the hydrogenation step. To set the first pressure value, a theoretical value up to which the hydrogen storage alloy can store hydrogen is obtained in advance. The theoretical value is calculated as an atomic weight ratio between hydrogen and the hydrogen storage alloy. Where the hydrogen storage alloy used is Mg2Ni, for example, Mg2Ni can theoretically store four H atoms, as indicated by the following reaction formula:

            Mg2Ni + 2H2 → Mg2NiH4



    [0013] The atomic weight of Mg is 24.3050, the atomic weight of Ni is 58.6934, and the atomic weight of H is 1.00794. Accordingly, the atomic weight ratio of hydrogen to Mg2Ni in Mg2NiH4 is given by

    and is found to be about 3.76 (wt%). In this manner, a hydrogen storage ratio of the hydrogen storage alloy to be used is obtained beforehand as the theoretical value.

    [0014] On the other hand, in the case of Mg6Ni being used as the hydrogen storage alloy, the reaction formula is as follows:

            Mg6Ni + 6H2 → Mg2NiH12



    [0015] Accordingly, the atomic weight ratio of hydrogen to Mg6Ni in Mg6NiH12 is given by

    and is found to be 5.91 (wt%).

    [0016] A pressure at which hydrogen is stored up to the theoretical value is set as the first pressure value. In FIG. 1, the pressure corresponding to a theoretical value of 4.5 wt% is 0.1 MPa. Thus, the pressure corresponding to the theoretical value is set as the first pressure value. The second pressure value is set as a value ten or more times greater than the first pressure value. In the example illustrated in FIG. 1, 2 MPa, which is 20 times as great as the first pressure value, is set as the second pressure value.

    [0017] The pressure in the hydrogen atmosphere is increased up to the second pressure value. Specifically, as the pressure in the hydrogen atmosphere rises above the first pressure value, more hydrogen is stored in excess of the theoretical value, and when the pressure in the hydrogen atmosphere is at a certain pressure value (in the example of FIG. 1, at around 0.3 MPa), the hydrogen storage ratio becomes almost constant (in the example of FIG. 1, about 6.2 wt%). The pressure in the hydrogen atmosphere is then further increased up to the second pressure value.

    [0018] After the second pressure value is reached, the dehydrogenation step is executed. Specifically, the pressure in the hydrogen atmosphere is lowered from the second pressure value to or below the first pressure value. In the example of FIG. 1, the pressure is decreased to 0.01 MPa, which equals 1/10 of the first pressure value. It should be noted here that as the pressure in the hydrogen atmosphere decreases below the first pressure value, the hydrogen storage alloy begins to store hydrogen again. At the lowest pressure 0.01 MPa, about 4.5 wt% of hydrogen is stored.

    [0019] Subsequently, the hydrogenation step is again executed, and as a result, more hydrogen is stored in the hydrogen storage alloy. Also in the second hydrogenation step, the pressure in the hydrogen atmosphere is raised up to the second pressure value. Then, also in the second dehydrogenation step, the pressure in the hydrogen atmosphere is lowered to the same pressure as in the first dehydrogenation step. As the hydrogenation and dehydrogenation steps are repeated thereafter, more and more hydrogen is stored in the hydrogen storage alloy, and the hydrogen storage ratio finally comes to follow a stable locus on the graph. In other words, the graph showing the relationship between the hydrogen storage ratio and the pressure in the hydrogenation step becomes nearly coincident with that showing the same relationship in the dehydrogenation step. At this stage, when the pressure in the hydrogen atmosphere is set at the first pressure value, about 20 wt% of hydrogen can be stored in the hydrogen storage alloy.

    [0020] Thus, according to the present invention, hydrogen storage alloys can store hydrogen in excess of their theoretical values by repeatedly executing the hydrogenation step and the dehydrogenation step, and this was confirmed by experiment.

    [0021] In conducting the experiment, particulate hydrogen storage alloy having a particle sized in less than 10nm was used. Specifically, the hydrogen storage alloy used was in particulate form with a particle size of 5 nm or less. By using hydrogen storage alloy with a small particle size, it is possible to lower the first pressure value, and since the second pressure value lowers correspondingly, it is unnecessary to apply a very high pressure for the storage of hydrogen (hydrogen can be stored in a low-pressure environment). Also, the temperature in the hydrogen atmosphere can be set at a low temperature. Moreover, it is possible to shorten the time for the storage of hydrogen. Specifically, the hydrogenation step and the dehydrogenation step, which hitherto required 120 minutes to 160 minutes each, can individually be completed in about 90 minutes.


    Claims

    1. A hydrogen storage method comprising:

    a hydrogenation step of hydrogenating a hydrogen storage alloy of Mg2Ni or Mg6Ni while increasing pressure in an atmosphere; and

    a dehydrogenation step of dehydrogenating the hydrogenated hydrogen storage alloy while decreasing the pressure in the atmosphere, wherein:

    in the hydrogenation step, a hydrogen storage ratio calculated as an atomic weight ratio between hydrogen and the hydrogen storage alloy is obtained beforehand as a theoretical value, a pressure at which the hydrogen storage alloy stores hydrogen up to the theoretical value is set as a first pressure value, a pressure value ten or more times greater than the first pressure value is set as a second pressure value, and the pressure in the atmosphere is increased up to the second pressure value,

    in the dehydrogenation step, the pressure in the atmosphere is decreased from the second pressure value to or below the first pressure value, and

    the hydrogenation step and the dehydrogenation step are repeatedly executed.


     
    2. The hydrogen storage method according to claim 1, wherein the hydrogen storage alloy has a particle sized in less than 10nm.
     


    Ansprüche

    1. Wasserstoffspeicherverfahren, das Folgendes umfasst:

    einen Hydrierungsschritt zum Hydrieren einer Wasserstoffspeicherlegierung aus Mg2Ni oder Mg6Ni, während der Druck in einer Atmosphäre erhöht wird; und

    einen Dehydrierungsschritt zum Dehydrieren der hydrierten Wasserstoffspeicherlegierung, während der Druck in der Atmosphäre gesenkt wird, wobei:

    in dem Hydrierungsschritt ein Hydrierungsspeicherverhältnis, das als ein Atomgewichtsverhältnis zwischen Wasserstoff und der Wasserstoffspeicherlegierung im Voraus als ein theoretischer Wert erhalten wird, berechnet wird, ein Druck, bei dem die Wasserstoffspeicherlegierung Wasserstoff bis zu dem theoretischen Wert speichert, als ein erster Druckwert eingestellt wird, ein Druckwert, der zehnmal oder mehr größer als der erste Druckwert ist, als ein zweiter Druckwert eingestellt wird und der Druck in der Atmosphäre bis zu dem zweiten Druckwert erhöht wird,

    in dem Dehydrierungsschritt der Druck in der Atmosphäre von dem zweiten Druckwert auf den ersten Druckwert oder darunter abgesenkt wird und

    der Hydrierungsschritt und der Dehydrierungsschritt wiederholt ausgeführt werden.


     
    2. Wasserstoffspeicherverfahren nach Anspruch 1, wobei die Wasserstoffspeicherlegierung eine Partikelgröße von weniger als 10 nm besitzt.
     


    Revendications

    1. Procédé de stockage d'hydrogène comprenant :

    une étape d'hydrogénation consistant à hydrogéner un alliage de stockage d'hydrogène de Mg2Ni ou Mg6Ni tout en augmentant la pression dans une atmosphère ; et

    une étape de déshydrogénation consistant à déshydrogéner l'alliage de stockage d'hydrogène hydrogéné tout en diminuant la pression dans l'atmosphère, dans lequel :

    dans l'étape d'hydrogénation, un rapport de stockage d'hydrogène calculé comme un rapport atomique pondéral entre l'hydrogène et l'alliage de stockage d'hydrogène est obtenu au préalable à titre de valeur théorique, une pression à laquelle l'alliage de stockage hydrogène stocke de l'hydrogène jusqu'à la valeur théorique est fixée à titre de première valeur de pression, une valeur de pression dix fois plus élevée, ou encore plus, que la première valeur de pression est fixée à titre de seconde valeur de pression, et la pression dans l'atmosphère est augmentée jusqu'à la seconde valeur de pression,

    dans l'étape de déshydrogénation, la pression dans l'atmosphère est diminuée depuis la seconde valeur de pression jusqu'à la première valeur de pression ou au-dessous, et

    l'étape d'hydrogénation et l'étape de déshydrogénation sont exécutées de façon répétée.


     
    2. Procédé de stockage d'hydrogène selon la revendication 1, dans lequel l'alliage de stockage hydrogène présente des particules de taille inférieure à 10 nm.
     




    Drawing








    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description