JP4415105B2 - Hydrogen storage material - Google Patents

Hydrogen storage material Download PDF

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JP4415105B2
JP4415105B2 JP2004155393A JP2004155393A JP4415105B2 JP 4415105 B2 JP4415105 B2 JP 4415105B2 JP 2004155393 A JP2004155393 A JP 2004155393A JP 2004155393 A JP2004155393 A JP 2004155393A JP 4415105 B2 JP4415105 B2 JP 4415105B2
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hydrogen
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hydrogen storage
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JP2005334739A (en
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鋭涛 王
強 徐
哲 清林
信宏 栗山
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National Institute of Advanced Industrial Science and Technology AIST
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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
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    • Y02E60/32—Hydrogen storage

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Description

本発明は、水素貯蔵材料及び水素貯蔵方法に関する。   The present invention relates to a hydrogen storage material and a hydrogen storage method.

水素は、資源としての豊富さ、環境に対する優しさ等から、将来の理想的な燃料として注目されている。水素を燃料として利用する場合の主な難点は、水素貯蔵の問題である。水素の貯蔵方法としては、高圧を利用する方法（下記非特許文献１参照）、低温における水素貯蔵方法（下記非特許文献２参照）等が報告されている。しかしながら、これらの高圧や低温を利用する方法は、安全面、容積、コストなどの点で制約が大きく、自動車用燃料などの貯蔵方法としては実用的な方法ではない。このことは、自動車用燃料等の用途に有用な固体水素貯蔵材料に対する広範な研究開発を促進してきた大きな要因といえる。   Hydrogen is attracting attention as an ideal fuel in the future because of its abundance as a resource and environmental friendliness. The main difficulty in using hydrogen as a fuel is the problem of hydrogen storage. As a method for storing hydrogen, a method using high pressure (see Non-Patent Document 1 below), a hydrogen storage method at a low temperature (see Non-Patent Document 2 below), and the like have been reported. However, these high-pressure and low-temperature methods are severely limited in terms of safety, volume and cost, and are not practical methods for storing automobile fuel and the like. This is a major factor that has promoted extensive research and development on solid hydrogen storage materials useful for applications such as automotive fuel.

これまで、水素を貯蔵するための固体キャリアとして、金属水素化物（下記非特許文献３及び４参照）、活性炭及びカーボンナノチューブ（下記非特許文献５及び６参照）等が研究されてきた。更に、最近、化学的水素貯蔵材料として、アラネート（下記非特許文献７参照）、リチウム−窒素系材料（下記非特許文献８参照）等が報告されている。   Heretofore, metal hydrides (see Non-Patent Documents 3 and 4 below), activated carbon, carbon nanotubes (see Non-Patent Documents 5 and 6 below), and the like have been studied as solid carriers for storing hydrogen. Furthermore, recently, as a chemical hydrogen storage material, alanate (refer to the following non-patent document 7), lithium-nitrogen-based material (refer to the following non-patent document 8), and the like have been reported.

この様に、水素貯蔵材料については、各種の研究が進められているが、高い重量水素密度と十分な水素解離エネルギーを有し、且つ、自動車用燃料等の用途で要求される高い安全性、低コスト、十分な水素放出・充填速度、取り扱い安さなどの条件を満たす材料は、いまだ見出されていないのが現状である。
F. Mitlitsky, A. H. Weisberg and B. Myers; Proc. of the 2000 U. S. DOE Hydrogen Program Review, NREL/CP-570-28890 (2001) 古浜庄一、太田時男監修、水素エネルギー最先端技術（１９９５）、エヌ・テイー・エス 上原斎、田村英雄監修、水素吸蔵合金−基礎から最先端技術まで,（１９９８）、エヌ・テイー・エス 太田時男監修、水素エネルギー最先端技術（１９９５）、エヌ・テイー・エス C. Zandonella, Nature, 410 (2001), 734; A. Zuttel, S. Orimo, MRS Bull, (2002), 705. B. Bogdanovic, M. Schwictrardi, J. Alloys Comp., 253-254, (1997), 1 P. Chen, Z. Xiong, J. Luo, J. Lin, K.L. Tan, Nature, 420 (2002), 302 As described above, various studies have been conducted on the hydrogen storage material, which has a high weight hydrogen density and sufficient hydrogen dissociation energy, and has high safety required for applications such as automobile fuel, At present, no material that satisfies the requirements of low cost, sufficient hydrogen release / filling speed, and ease of handling has been found.
F. Mitlitsky, AH Weisberg and B. Myers; Proc. Of the 2000 US DOE Hydrogen Program Review, NREL / CP-570-28890 (2001) Supervised by Shoichi Furuhama and Tokio Ota, Advanced Hydrogen Energy Technology (1995), NTS Supervised by Sae Uehara and Hideo Tamura, Hydrogen storage alloys-from basic to advanced technology, (1998), NT Supervised by Tokio Ota, Advanced Hydrogen Energy Technology (1995), NTS C. Zandonella, Nature, 410 (2001), 734; A. Zuttel, S. Orimo, MRS Bull, (2002), 705. B. Bogdanovic, M. Schwictrardi, J. Alloys Comp., 253-254, (1997), 1 P. Chen, Z. Xiong, J. Luo, J. Lin, KL Tan, Nature, 420 (2002), 302

本発明は、上記した従来技術の現状に鑑みてなされたものであり、その主な目的は、豊富に存在する低コストの物質を有効成分とする可逆的な水素貯蔵材料であって、高い安全性を有し、且つ十分な水素放出・充填速度と取り扱い安さなどの条件を満足できる新規な水素貯蔵材料を提供することである。   The present invention has been made in view of the current state of the prior art described above, and its main object is a reversible hydrogen storage material containing an abundant low-cost substance as an active ingredient, which is highly safe. It is an object of the present invention to provide a novel hydrogen storage material that has the characteristics and satisfies the conditions such as sufficient hydrogen release / filling speed and ease of handling.

本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、安全性が高く入手の容易な物質であるＮａ2Ｏは、一定の条件下において水素を吸収して水酸化ナト
リウムと水素化ナトリウムに変化し、更に、形成された水酸化ナトリウムと水素化ナトリ
ウムの混合物は、水素吸収の際の条件と比較して低い水素圧力又は高温度とすることによって、水素を放出して再度Ｎａ2Ｏとなり、可逆的な水素の吸収と放出が可能であるとい
う、従来全く知られていないＮａ2Ｏの新規な特性を見出した。そして、斯かるＮａ2Ｏの特性を利用することによって、安全で、取り扱いの容易な新規な水素貯蔵材料が得られることを見出し、ここに本発明を完成するに至った。 The present inventor has intensively studied to achieve the above-described object. As a result, Na 2 O, which is a highly safe and easily available material, absorbs hydrogen under certain conditions and changes into sodium hydroxide and sodium hydride. The mixture of sodium hydride releases hydrogen and becomes Na 2 O again by setting the hydrogen pressure or temperature lower than the conditions for hydrogen absorption, so that reversible absorption and release of hydrogen is possible. The inventors have found a novel characteristic of Na 2 O that has never been known. The inventors have found that a novel hydrogen storage material that is safe and easy to handle can be obtained by utilizing such characteristics of Na 2 O, and the present invention has been completed here.

即ち、本発明は、下記の水素貯蔵材料及び水素貯蔵方法を提供するものである。
１． Ｎａ2Ｏを有効成分として含有することを特徴とする水素貯蔵材料。
２． 更に、ＮａＨとＮａＯＨを含有する上記項１に記載の水素貯蔵材料。
３． 更に、Ｓｉ、Ｔｉ、Ｚｒ、Ｆｅ、Ｎｉ、Ｃｒ及びこれらの元素を含有する化合物からなる群から選ばれた少なくとも一種の成分を含有する上記項１又は２に記載の水素貯蔵材料。
４． 上記項１〜３のいずれかに記載の水素貯蔵材料を水素と接触させることを特徴とする水素貯蔵方法。
５． −５０℃以上、５００℃未満の温度範囲、１．３Ｐａ〜５０ＭＰａの水素圧力下で、水素貯蔵材料と水素とを接触させることを特徴とする上記項４に記載の水素貯蔵方法。６． 上記項１〜３のいずれかに記載の水素貯蔵材料を水素と接触させて該水素貯蔵材料に水素を吸収させることによる水素貯蔵と、この反応によって形成されるＮａＨとＮａＯＨから水素を発生させることによる水素放出を可逆的に行うことを特徴とする水素の貯蔵及び放出方法。
７． 水素貯蔵材料への水素吸収反応を、１．３Ｐａ〜５０ＭＰａの水素圧下において、−５０℃以上５００℃未満の温度範囲で行い、水素放出反応を水素吸収反応より高い温度条件下及び／又は低い水素圧下で行う上記項６に記載の水素の貯蔵及び放出方法。

本発明の水素貯蔵材料は、Ｎａ2Ｏを有効成分とするものである。本発明者の研究によ
れば、Ｎａ2Ｏは、下記（１）式に従って水素を吸収して、ＮａＨとＮａＯＨに変化する
ことが明らかとなった。これは、従来全く知られていないＮａ2Ｏの特性である。 That is, the present invention provides the following hydrogen storage material and hydrogen storage method.
1. A hydrogen storage material comprising Na 2 O as an active ingredient.
2. Item 2. The hydrogen storage material according to Item 1, further comprising NaH and NaOH.
3. Item 3. The hydrogen storage material according to Item 1 or 2, further comprising at least one component selected from the group consisting of Si, Ti, Zr, Fe, Ni, Cr, and compounds containing these elements.
4). A hydrogen storage method according to any one of Items 1 to 3, wherein the hydrogen storage material is brought into contact with hydrogen.
5). 5. The hydrogen storage method according to item 4, wherein the hydrogen storage material and hydrogen are brought into contact under a temperature range of −50 ° C. or higher and lower than 500 ° C. under a hydrogen pressure of 1.3 Pa to 50 MPa. 6). Hydrogen storage by bringing the hydrogen storage material according to any one of Items 1 to 3 into contact with hydrogen and allowing the hydrogen storage material to absorb hydrogen, and generating hydrogen from NaH and NaOH formed by this reaction A method for storing and releasing hydrogen, characterized in that hydrogen release by reversible is performed reversibly.
7). The hydrogen absorption reaction to the hydrogen storage material is performed in a temperature range of −50 ° C. or more and less than 500 ° C. under a hydrogen pressure of 1.3 Pa to 50 MPa, and the hydrogen release reaction is performed under higher temperature conditions and / or lower hydrogen than the hydrogen absorption reaction. Item 7. The method for storing and releasing hydrogen according to Item 6, which is performed under pressure.

The hydrogen storage material of the present invention contains Na 2 O as an active ingredient. According to the study by the present inventor, it has become clear that Na 2 O absorbs hydrogen according to the following formula (1) and changes into NaH and NaOH. This is a characteristic of Na 2 O which has not been known at all.

Ｎａ2Ｏ ＋ Ｈ2 → ＮａＨ ＋ ＮａＯＨ （１）
本発明の水素貯蔵材料の有効成分であるＮａ2Ｏは、公知化合物であり、密度２．３ｇ
／ｃｍ3の無色物質である。本発明の水素貯蔵材料では、有効成分として用いるＮａ2Ｏの種類について特に限定はなく、一般に市販されているものをそのまま使用できる。また、ボールミルなどを用いて、適度な大きさに粉砕したものを用いても良い。 Na 2 O + H 2 → NaH + NaOH (1)
Na 2 O which is an active ingredient of the hydrogen storage material of the present invention is a known compound and has a density of 2.3 g.
/ Cm 3 colorless material. The hydrogen storage material of the present invention is not particularly limited about the kind of Na 2 O is used as an active ingredient, generally those that are commercially available can be used as it is. Moreover, you may use what was grind | pulverized to the moderate magnitude | size using a ball mill etc.

また、後述する様に、Ｎａ2Ｏの水素の吸収・放出は可逆的であり、Ｎａ2Ｏの水素吸収によって形成されるＮａＨとＮａＯＨの混合物は、加熱や減圧によって水素を放出して、Ｎａ2Ｏに変化する。従って、本発明では、ＮａＨとＮａＯＨを原料として、この混合物
から水素を放出して形成されるＮａ2Ｏを水素貯蔵材料の有効成分として用いても良い。 Further, as will be described later, the absorption and release of Na 2 O hydrogen is reversible, and the mixture of NaH and NaOH formed by the absorption of Na 2 O hydrogen releases hydrogen by heating or reduced pressure, and Na Change to 2 O. Therefore, in the present invention, Na 2 O formed by releasing hydrogen from this mixture using NaH and NaOH as raw materials may be used as an active ingredient of the hydrogen storage material.

本発明の水素貯蔵材料は、有効成分であるＮａ2Ｏを含有すればよく、水素貯蔵性能に
悪影響の無い限りその他の成分が同時に含まれていても良い。通常は、水素の吸収反応が進行することにより、上記（１）式によってＮａＨとＮａＯＨが形成されるので、水素の貯蔵過程では、Ｎａ2Ｏ、ＮａＨ及びＮａＯＨが同時に存在することになる。また、有効
成分として存在するＮａ2Ｏが完全に水素を吸収した場合には、Ｎａ2Ｏは、全てＮａＨとＮａＯＨに変換された状態となる。理論的には、Ｎａ2Ｏが完全に水素を吸収した場合に
は、吸収された水素とＮａ2Ｏ の合計量を１００重量部として、３．１３重量部の水素を貯蔵することが可能である。 Hydrogen storage material of the present invention may be contained Na 2 O as an active ingredient, other ingredients may be included at the same time unless adverse effect on hydrogen storage capacity. Normally, when the hydrogen absorption reaction proceeds, NaH and NaOH are formed according to the above equation (1), so that Na 2 O, NaH, and NaOH exist simultaneously in the hydrogen storage process. Further, when Na 2 O present as an active ingredient has completely absorbed hydrogen, Na 2 O is converted into NaH and NaOH. Theoretically, when Na 2 O has completely absorbed hydrogen, it is possible to store 3.13 parts by weight of hydrogen, with the total amount of absorbed hydrogen and Na 2 O being 100 parts by weight. is there.

本発明の水素貯蔵材料による水素吸収（充填）時の温度は、通常、５００℃未満とすればよい。水素吸収温度の下限については、特に限定的ではなく、例えば、−５０℃程度の
温度においても水素吸収（貯蔵）が可能であるが、１５℃程度以上とすることにより、水素の吸収速度を上昇させることができる。特に、６０〜３５０℃程度とすることにより、適度な速度で水素の吸収反応を進行させることができる。 The temperature at the time of hydrogen absorption (filling) by the hydrogen storage material of the present invention may be usually less than 500 ° C. The lower limit of the hydrogen absorption temperature is not particularly limited. For example, hydrogen absorption (storage) is possible even at a temperature of about −50 ° C., but by increasing the temperature to about 15 ° C. or higher, the hydrogen absorption rate is increased. Can be made. In particular, by setting the temperature to about 60 to 350 ° C., the hydrogen absorption reaction can proceed at an appropriate rate.

水素吸収（充填）時の水素圧についても特に限定的ではなく、例えば、１．３Ｐａ〜５０ＭＰａ程度の水素圧において水素の吸収反応を進行させることが可能であるが、適度な速度で水素吸収反応を進行させるためには、０．１ＭＰａ〜１０ＭＰａ程度の水素圧とすることが好ましく、０．５ＭＰａ〜５ＭＰａ程度の水素圧とすることがより好ましい。   The hydrogen pressure at the time of hydrogen absorption (filling) is not particularly limited. For example, the hydrogen absorption reaction can proceed at a hydrogen pressure of about 1.3 Pa to 50 MPa, but the hydrogen absorption reaction at an appropriate rate. In order to proceed, the hydrogen pressure is preferably about 0.1 MPa to 10 MPa, more preferably about 0.5 MPa to 5 MPa.

図１は、本発明の水素貯蔵材料の有効成分であるＮａ2Ｏ及びその水素吸収過程におけ
る生成物の粉末Ｘ線回折（ＸＲＤ）パターンを示す図面である。図１ａは、Ｎａ2ＯのＸ
線回折パターンであり、図１ｂは、Ｎａ2Ｏを６０℃で１０ＭＰａの水素と４８時間接触
させた試料のＸ線回折パターンである。図１ｂからは、ＮａＨとＮａＯＨに帰属する回折ピークが観察され、約５０％の転化率でＮａＨとＮａＯＨに変化したことが判る。 FIG. 1 is a diagram showing a powder X-ray diffraction (XRD) pattern of Na 2 O, which is an active ingredient of the hydrogen storage material of the present invention, and a product in the hydrogen absorption process. FIG. 1a shows the X of Na 2 O
FIG. 1b is an X-ray diffraction pattern of a sample obtained by contacting Na 2 O with 10 MPa hydrogen at 60 ° C. for 48 hours. From FIG. 1b, it can be seen that diffraction peaks attributed to NaH and NaOH were observed, and that they changed to NaH and NaOH at a conversion of about 50%.

図１ｃは、Ｎａ2Ｏを１５０℃で１０ＭＰａの水素と６０時間接触させた試料のＸ線回
折パターンである。また、図１ｄは、ＮａＨとＮａＯＨの１：１（モル比）混合物のＸ線回折パターンである。図１ｃでは、Ｎａ2Ｏに帰属する回折ピークがほとんど消失し、Ｎ
ａＨとＮａＯＨに帰属する回折ピークのみが観察される。これから、約１００％の添加率でＮａＨとＮａＯＨに変化したことが判る。また、水素吸収量測定から、吸収された水素とＮａ2Ｏの合計量を１００重量部として約３重量部の水素が吸収されたことがわかる。 FIG. 1c is an X-ray diffraction pattern of a sample obtained by contacting Na 2 O with 10 MPa hydrogen at 150 ° C. for 60 hours. FIG. 1d is an X-ray diffraction pattern of a 1: 1 (molar ratio) mixture of NaH and NaOH. In FIG. 1c, the diffraction peak attributed to Na 2 O almost disappears, and N
Only diffraction peaks attributed to aH and NaOH are observed. From this, it can be seen that the concentration changed to NaH and NaOH at an addition rate of about 100%. Further, from the hydrogen absorption measurement, it is understood that about 3 parts by weight of hydrogen was absorbed with the total amount of absorbed hydrogen and Na 2 O being 100 parts by weight.

更に、本発明者の研究によれば、上記（１）式に従ってＮａ2Ｏが水素を吸収して形成
されるＮａＨとＮａＯＨは、下記（２）式に従って、水素を放出して、再度Ｎａ2Ｏに変
化することが明らかになった。 Further, according to the research of the present inventor, NaH and NaOH formed by Na 2 O absorbing hydrogen according to the above formula (1) release hydrogen according to the following formula (2), and again Na 2. It became clear that it changed to O.

ＮａＨ ＋ ＮａＯＨ → Ｎａ2Ｏ ＋ Ｈ2 （２）
図２は、ＮａＨとＮａＯＨのモル比１：１混合物を、昇温速度２℃／分で昇温した場合の熱重量測定（ＴＧ）の結果を示すグラフである。図２から、ＮａＨとＮａＯＨの混合物を加熱した場合に、１６０℃から重量が徐々に減少し、２２０℃付近から重量減少が著しくなることが判る。また、重量減少はＮａＨとＮａＯＨの合計量を基準として３．１重量％に達し、理論値におけるすべての水素が放出されたことが確認できた。 NaH + NaOH → Na 2 O + H 2 (2)
FIG. 2 is a graph showing the results of thermogravimetry (TG) when a 1: 1 mixture of NaH and NaOH is heated at a heating rate of 2 ° C./min. From FIG. 2, it can be seen that when a mixture of NaH and NaOH is heated, the weight gradually decreases from 160 ° C., and the weight decrease becomes remarkable from around 220 ° C. Moreover, the weight reduction reached 3.1% by weight based on the total amount of NaH and NaOH, and it was confirmed that all the hydrogen in the theoretical value was released.

図３は、質量分析（ＭＳ）−ＴＰＤ(Temperature Programmed Desorption)法による脱
水素測定の結果を示すグラフである。図３ａは、ＮａＨとＮａＯＨのモル比１：１の混合物を、昇温速度２℃／分で昇温した場合についての測定結果を示すものであり、１６０℃付近からＨ2放出が顕著になり、２７３℃でＨ2の放出がピークに達することが確認できた。また、ＮａＨとＮａＯＨのモル比１：１混合物を３４０℃で、ポンプ（約１３．３Ｐａ）を用いて２４時間排気したのち、ＸＲＤを測定した結果、ＮａＨ及びＮａＯＨに帰属する回折ピークが消失し、Ｎａ2Ｏに帰属するピークが観測された。この結果からは、Ｎａ
Ｈ及びＮａＯＨの混合物は、水素を放出してＮａ2Ｏに変化することが確認できた。 FIG. 3 is a graph showing the results of dehydrogenation measurement by mass spectrometry (MS) -TPD (Temperature Programmed Desorption) method. FIG. 3a shows the measurement result when a mixture of NaH and NaOH having a molar ratio of 1: 1 is heated at a heating rate of 2 ° C./min, and H 2 release becomes remarkable from around 160 ° C. It was confirmed that the release of H 2 reached a peak at 273 ° C. Further, as a result of measuring XRD after evacuating a mixture of NaH and NaOH at a molar ratio of 1: 1 at 340 ° C. for 24 hours using a pump (about 13.3 Pa), diffraction peaks attributed to NaH and NaOH disappeared. , A peak attributed to Na 2 O was observed. From this result, Na
It was confirmed that the mixture of H and NaOH changed into Na 2 O by releasing hydrogen.

上記した（１）式と（２）式より、Ｎａ2Ｏを水素貯蔵材料とする場合に、下記（３）
式に従って水素の吸収と放出反応が可逆的に進行することが判る。 From the above formulas (1) and (2), when Na 2 O is used as a hydrogen storage material, the following (3)
It can be seen that the hydrogen absorption and release reactions proceed reversibly according to the equation.

Ｎａ2Ｏ ＋ Ｈ2 ⇔ ＮａＨ ＋ ＮａＯＨ （３）
本発明の水素貯蔵材料では、水素の放出反応させる際の温度については、特に限定的ではなく、例えば、−５０℃程度以上、５００℃程度未満の温度範囲において、水素を放出させることが可能であり、特に、１５℃〜４００℃程度、好ましくは８０℃〜３５０℃程度の温度範囲において、十分な速度で水素を放出することができる。 Na 2 O + H 2 ⇔ NaH + NaOH (3)
In the hydrogen storage material of the present invention, the temperature at which hydrogen is released is not particularly limited. For example, hydrogen can be released in a temperature range of about −50 ° C. or more and less than about 500 ° C. In particular, hydrogen can be released at a sufficient rate in a temperature range of about 15 ° C to 400 ° C, preferably about 80 ° C to 350 ° C.

尚、上記（３）式に示す様に、Ｎａ2Ｏの水素吸収・放出反応は可逆反応であることか
ら、水素吸収反応の際の条件より、高い温度及び低い水素圧のいずれか一方又は両方の条件を満足することによって、水素の放出反応を円滑且つ迅速に進行させることができる。 As shown in the above formula (3), since the hydrogen absorption / release reaction of Na 2 O is a reversible reaction, either one or both of a higher temperature and a lower hydrogen pressure than the conditions during the hydrogen absorption reaction. By satisfying this condition, the hydrogen release reaction can proceed smoothly and quickly.

本発明の水素貯蔵材料は、Ｎａ2Ｏに加えて、更に、Ｓｉ、Ｔｉ、Ｚｒ、Ｆｅ、Ｎｉ、
Ｃｒ及びこれらの元素を含有する化合物からなる群から選ばれた少なくとも一種の成分（以下、「添加成分」ということがある）を含有することができる。これらの添加成分を含む水素貯蔵材料は、特に優れた水素吸収性能を有するものとなり、Ｎａ2Ｏのみを有効成
分とする水素貯蔵材料と比較して、より低温度において、より急速な水素吸収が可能となる。 In addition to Na 2 O, the hydrogen storage material of the present invention further includes Si, Ti, Zr, Fe, Ni,
It can contain at least one component selected from the group consisting of Cr and compounds containing these elements (hereinafter sometimes referred to as “additional components”). The hydrogen storage material containing these additional components has particularly excellent hydrogen absorption performance, and more rapid hydrogen absorption at a lower temperature compared to a hydrogen storage material containing only Na 2 O as an active ingredient. It becomes possible.

また、Ｎａ2Ｏの水素吸収により形成されるＮａＨとＮａＯＨの混合物中に、上記した
添加成分が存在する場合には、水素の放出反応が著しく促進され、添加成分を含有しない場合と比較して、より低温度での急速な水素放出が可能となる。 In addition, when the above-described additive component is present in the mixture of NaH and NaOH formed by hydrogen absorption of Na 2 O, the hydrogen release reaction is remarkably accelerated, compared to the case where no additive component is contained. Rapid hydrogen release at lower temperatures is possible.

添加成分としては、Ｓｉ、Ｔｉ、Ｚｒ、Ｆｅ、Ｎｉ若しくはＣｒの金属単体、又はこれらの金属元素の少なくとも一種を含む化合物を用いることができる。添加成分は、一種単独又は二種以上混合して用いることができる。添加成分として用いる化合物の種類については、特に限定的ではなく、例えば、酸化物、塩化物、アルコキシド化合物、配位子を含む化合物等を用いることができる。特に、添加成分の内で、ＳｉＯ2、ＴｉＣｌ3、ＴｉＯ2、Ｔｉ（ＯＢｕ）4、ＺｒＯ2、Ｚｒ（ＯＰｒ）4，Ｆｅ2Ｏ3、Ｆｅ（ａｃａｃ）2、Ｎｉ
Ｏ, Ｎｉ(1,5-ＣＯＤ)2, Ｃｒ2Ｏ3（上記式中、ａｃａｃはアセチルアセトネート、Ｂｕ
はブチル、Ｐｒはプロピル、ＣＯＤはシクロオクタジエンを表す）等を用いる場合には、水素の吸収・放出が著しく促進される。 As the additive component, a simple substance of Si, Ti, Zr, Fe, Ni, or Cr, or a compound containing at least one of these metal elements can be used. An additive component can be used individually by 1 type or in mixture of 2 or more types. The type of the compound used as the additive component is not particularly limited, and for example, an oxide, chloride, alkoxide compound, a compound containing a ligand, or the like can be used. In particular, among the additive components, SiO 2 , TiCl 3 , TiO 2 , Ti (OBu) 4 , ZrO 2 , Zr (OPr) 4 , Fe 2 O 3 , Fe (acac) 2 , Ni
O, Ni (1,5-COD) 2 , Cr 2 O 3 (wherein acac is acetylacetonate, Bu
When butyl is used, Pr is propyl, COD is cyclooctadiene, etc., the absorption and release of hydrogen is remarkably accelerated.

添加成分は、単に、Ｎａ2Ｏと混合するだけでも良いが、Ｎａ2Ｏと添加成分とを混合し、ボールミルを用いて十分に撹拌することによって、Ｎａ2Ｏと添加成分が均一に混合さ
れて、水素の吸収・放出が著しく促進される。 The additive component may be simply mixed with Na 2 O, but by mixing Na 2 O and the additive component and thoroughly stirring using a ball mill, the Na 2 O and additive component are uniformly mixed. Thus, the absorption and release of hydrogen is significantly accelerated.

また、Ｎａ2Ｏと添加成分を混合することに代えて、ＮａＨとＮａＯＨの混合物に上記
した添加成分を加えても良い。この様にして得られるＮａＨ、ＮａＯＨ及び添加成分の混合物は、上記式（２）による水素放出反応が著しく促進されており、低温度における水素放出が可能である。更に、水素放出によって形成されるＮａ2Ｏは、添加成分を含有する
ものとなり、非常に優れた水素吸収特性を有するものとなる。 Also, instead of mixing the added ingredients and Na 2 O, it may be added components described above to a mixture of NaH and NaOH. In the mixture of NaH, NaOH and additive components obtained in this way, the hydrogen releasing reaction according to the above formula (2) is remarkably accelerated, and hydrogen releasing at a low temperature is possible. Further, Na 2 O formed by hydrogen release contains an additive component and has very excellent hydrogen absorption characteristics.

上記した添加成分の添加量は、Ｎａ2Ｏ １００ モルに対して０．０１〜１００モルの
程度とすることが好ましく、０．１〜１０モルの程度とすることがより好ましい。 The addition amount of the above-described additive component is preferably about 0.01 to 100 mol, more preferably about 0.1 to 10 mol, relative to 100 mol of Na 2 O.

図１ｅは、ＮａＨとＮａＯＨのモル比１：１の混合物にＮａＨ１００モルに対して５モルのＳｉＯ2を添加した試料を、３４０℃においてポンプで排気して１３．３Ｐａの圧力
下に３時間維持して得られた試料についての粉末Ｘ線回折パターンである。図１ｅからは、Ｎａ2Ｏに帰属する回折ピークが観察され、ＮａＨとＮａＯＨの混合物から、水素が放
出されてＮａ2Ｏが形成されたことが確認できる。また、図１ｆは、ＮａＨとＮａＯＨの
モル比１：１の混合物にＮａＨ１００モルに対して５モルのＳｉＯ2を添加した試料を、
３４０℃においてポンプで排気して１３．３Ｐａの圧力下に３時間維持し、その後１５０℃、水素圧４ＭＰａで水素を吸収させる操作を２回繰り返して得られた試料についての粉末Ｘ線回折パターンである。図１ｆからは、ＮａＨとＮａＯＨに帰属する回折ピークが観察され、水素の放出と吸収が可逆的に進行していることが確認できる。 FIG. 1e shows a sample in which 5 mol of SiO 2 is added to a mixture of NaH and NaOH at a molar ratio of 1: 1 to 100 mol of NaH and is pumped at 340 ° C. and maintained at a pressure of 13.3 Pa for 3 hours. It is a powder X-ray-diffraction pattern about the sample obtained by doing this. From FIG. 1e, a diffraction peak attributed to Na 2 O is observed, and it can be confirmed that hydrogen was released from the mixture of NaH and NaOH to form Na 2 O. FIG. 1 f shows a sample in which 5 mol of SiO 2 is added to 100 mol of NaH to a mixture of NaH and NaOH at a molar ratio of 1: 1.
A powder X-ray diffraction pattern of a sample obtained by evacuating with a pump at 340 ° C. and maintaining it under a pressure of 13.3 Pa for 3 hours and then absorbing hydrogen at 150 ° C. and a hydrogen pressure of 4 MPa twice. is there. From FIG. 1f, diffraction peaks attributed to NaH and NaOH are observed, and it can be confirmed that the release and absorption of hydrogen proceed reversibly.

図３ｂは、ＮａＨとＮａＯＨのモル比１：１の混合物にＮａＨ１００モルに対して５モルのＳｉＯ2を添加した添加した試料を、昇温速度２℃／分で昇温した場合について、Ｍ
Ｓ−ＴＰＤ法による脱水素測定の結果を示すグラフである。このグラフから、Ｈ2の放出
ピークが２４３℃に観察され、ＮａＨとＮａＯＨのモル比１：１の混合物のみを用いる場合（曲線ａ）と比較して、水素放出温度が約３０℃低温にシフトしたことが確認できる。 FIG. 3b shows a case where a sample prepared by adding 5 moles of SiO 2 to 100 moles of NaH in a 1: 1 mixture of NaH and NaOH is heated at a heating rate of 2 ° C./min.
It is a graph which shows the result of the dehydrogenation measurement by S-TPD method. From this graph, the H 2 release peak is observed at 243 ° C., and the hydrogen release temperature is shifted to about 30 ° C. lower than when only a 1: 1 mixture of NaH and NaOH is used (curve a). It can be confirmed.

本発明の水素貯蔵材料は、安価で豊富に存在し、安全性の高いＮａ2Ｏを有効成分とす
るものであり、更に、Ｎａ2Ｏの水素吸収によって形成されるＮａＨとＮａＯＨも安全性
が高く、取り扱いが容易な物質である。また、本発明の水素貯蔵材料は、水素の吸収と放出を繰り返し行っても、殆ど水素貯蔵性能が低下せず、高いリサイクル性を持つ材料である。 The hydrogen storage material of the present invention is inexpensive and abundant, and has high safety Na 2 O as an active ingredient. Further, NaH and NaOH formed by hydrogen absorption of Na 2 O are also safe. It is high and easy to handle. In addition, the hydrogen storage material of the present invention is a material having a high recyclability with little deterioration in hydrogen storage performance even when hydrogen absorption and release are repeated.

従って、本発明の水素貯蔵材料は、低コストで、安全性が高く取り扱いが容易な、非常に有用性の高い水素貯蔵材料である。   Therefore, the hydrogen storage material of the present invention is a highly useful hydrogen storage material that is low in cost, safe and easy to handle.

本発明の水素貯蔵材料は、水素が必要とされる広範囲の環境下において使用することができる。例えば、自動車、船舶、航空機、ミサイル用等のオンボード水素貯蔵等の水素貯蔵器として有効に利用することができる。また、水素燃料電池への水素供給用水素貯蔵器としての応用も可能である。   The hydrogen storage material of the present invention can be used in a wide range of environments where hydrogen is required. For example, it can be effectively used as a hydrogen storage device for onboard hydrogen storage for automobiles, ships, aircraft, missiles, and the like. Further, it can be applied as a hydrogen reservoir for supplying hydrogen to a hydrogen fuel cell.

更に、本発明の水素貯蔵材料を容器中に収納することによって、容易に水素貯蔵器を得ることができる。この様な水素貯蔵器は、例えば、エネルギー運搬の用途に利用することもできる。   Furthermore, by storing the hydrogen storage material of the present invention in a container, a hydrogen storage device can be easily obtained. Such a hydrogen storage can be used for, for example, energy transportation.

以下、実施例を挙げて本発明を更に詳細に説明する。   Hereinafter, the present invention will be described in more detail with reference to examples.

実施例１
Na2O 248 mg (4 mmol)を容積2.3 mlの試料セルに入れ、水素吸収・放出量測定装置に接続し、60℃で10 MPaの水素を導入した。48時間後に、吸収された水素とNa2Oの合計量を基準として1.5 wt%の水素吸収が観測された。粉末ＸＲＤを測定した結果、Na2O に帰属するピークの他、NaHとNaOHに帰属するピークが観測され、約50%のNa2Oが未反応のままで残り、約50%のNa2OがNaHとNaOHに変化したことがわかった。 Example 1
Na 2 O 248 mg (4 mmol) was placed in a sample cell with a volume of 2.3 ml, connected to a hydrogen absorption / release measurement device, and 10 MPa hydrogen was introduced at 60 ° C. After 48 hours, 1.5 wt% hydrogen absorption was observed based on the total amount of absorbed hydrogen and Na 2 O. As a result of measuring powder XRD, a peak attributed to Na 2 O was observed in addition to a peak attributed to Na 2 O, and about 50% Na 2 O remained unreacted, and about 50% Na 2 O Turned out to be NaH and NaOH.

実施例２
Na2O 248 mg (4 mmol)を容積2.3 mlの試料セルに入れ、水素吸収・放出量測定装置に接続し、150℃で10 MPaの水素を導入した。60時間後に、吸収された水素とNa2Oの合計量を基
準として、3.0 wt%の水素が吸収された。粉末ＸＲＤを測定した結果、Na2O に帰属するピークが殆ど消失し、NaHとNaOHに帰属するピークが観測され、Na2Oがほぼ100%の転化率でNaHとNaOHに変化したことがわかった。 Example 2
Na 2 O 248 mg (4 mmol) was put in a sample cell with a volume of 2.3 ml, connected to a hydrogen absorption / release measurement apparatus, and 10 MPa hydrogen was introduced at 150 ° C. After 60 hours, 3.0 wt% hydrogen was absorbed based on the total amount of absorbed hydrogen and Na 2 O. As a result of measuring powder XRD, it was found that most of the peaks attributed to Na 2 O disappeared, peaks attributed to NaH and NaOH were observed, and Na 2 O changed to NaH and NaOH at a conversion rate of almost 100%. It was.

実施例３
実施例２における水素吸収後の試料を340℃でポンプ(約１３．３Ｐａ)を用いて３時間排
気したのち、再び150℃で10 MPaの水素を導入した。60時間後に、吸収された水素とNa2O
の合計量を基準として、2.3 wt%の水素が再吸収されたことが確認できた。 Example 3
The sample after absorbing hydrogen in Example 2 was evacuated at 340 ° C. using a pump (about 13.3 Pa) for 3 hours, and 10 MPa of hydrogen was again introduced at 150 ° C. After 60 hours, absorbed hydrogen and Na 2 O
It was confirmed that 2.3 wt% of hydrogen was reabsorbed based on the total amount of hydrogen.

実施例４
Na2OとSiO2の混合物（Na2O：SiO2（モル比）＝１００：５）をボールミルに入れ、回転速度300rpm、回転時間10分間、停止時間10分間の繰り返し条件で３時間混合した。このよう
に調製した試料260 mgを2.3 mlの試料セルに入れ、水素吸収・放出量測定装置に接続し、150℃で4.0 MPaの水素を導入した。3時間後に、吸収された水素とNa2O/SiO2混合物の合計量を基準として2.9 wt%の水素が吸収されたことが確認できた。次いで、340℃でポンプ(
約１３．３Ｐａ)を用いて３時間排気したのち、再び150℃で4.0 MPaの水素を導入した。3時間後に、2.9 wt%の水素が再吸収されたことが確認できた。 Example 4
A mixture of Na 2 O and SiO 2 (Na 2 O: SiO 2 (molar ratio) = 100: 5) was placed in a ball mill and mixed for 3 hours under a repetition condition of a rotation speed of 300 rpm, a rotation time of 10 minutes, and a stop time of 10 minutes. . 260 mg of the sample thus prepared was placed in a 2.3 ml sample cell, connected to a hydrogen absorption / release measurement apparatus, and hydrogen at 4.0 MPa was introduced at 150 ° C. After 3 hours, it was confirmed that 2.9 wt% of hydrogen was absorbed based on the total amount of absorbed hydrogen and Na 2 O / SiO 2 mixture. Next, the pump (
After evacuating for 3 hours using about 13.3 Pa), 4.0 MPa of hydrogen was again introduced at 150 ° C. After 3 hours, it was confirmed that 2.9 wt% of hydrogen was reabsorbed.

実施例５
回転速度300rpm、回転時間10分間、停止時間10分間の繰り返し条件で、ＮａＨとＮａＯＨのモル比１：１混合物を３時間ボールミルで混合した。このように調製した試料256 mgを容積2.3 mlの試料セルに入れ、水素吸収・放出量測定装置に接続した。340℃でポンプ(約１３．３Ｐａ)を用いて３時間排気したのち、150℃で10 MPaの水素を導入した。60時間後に、用いたＮａＨとＮａＯＨの合計量を基準として2.2wt%の水素が再吸収されたことが確認できた。 Example 5
Under a repetition condition of a rotation speed of 300 rpm, a rotation time of 10 minutes, and a stop time of 10 minutes, a 1: 1 molar ratio mixture of NaH and NaOH was mixed with a ball mill for 3 hours. 256 mg of the sample thus prepared was placed in a sample cell having a volume of 2.3 ml and connected to a hydrogen absorption / release amount measuring apparatus. After evacuating for 3 hours at 340 ° C. using a pump (about 13.3 Pa), 10 MPa hydrogen was introduced at 150 ° C. After 60 hours, it was confirmed that 2.2 wt% of hydrogen was reabsorbed based on the total amount of NaH and NaOH used.

実施例６
ＮａＨとＮａＯＨのモル比１：１混合物に、ＮａＨ１００モルに対して５モルの割合でＳｉＯ2を添加し、この混合物をボールミルに入れ、回転速度300rpm、回転時間10分間、停
止時間10分間の繰り返し条件で３時間混合した。 Example 6
NaH and NaOH molar ratio of 1: 1 mixture was added SiO 2 at a ratio of 5 moles relative NaH100 mol, the mixture was put into a ball mill, the rotational speed 300 rpm, rotation time 10 minutes, repeating the stopping time 10 minutes The mixture was mixed for 3 hours.

このように調製した試料268 mgを容積2.3 mlの試料セルに入れ、水素吸収・放出量測定装置に接続した。340℃でポンプ(約１３．３Ｐａ)を用いて３時間排気したのち、150℃で4.0 MPaの水素を導入した。3時間後に、用いたＮａＨ、ＮａＯＨ及びＳｉＯ2の合計量を
基準として2.9wt%の水素吸収が観測された。 268 mg of the sample prepared in this way was placed in a sample cell having a volume of 2.3 ml and connected to a hydrogen absorption / release amount measuring device. After evacuating for 3 hours at 340 ° C. using a pump (about 13.3 Pa), hydrogen at 4.0 MPa was introduced at 150 ° C. After 3 hours, 2.9 wt% hydrogen absorption was observed based on the total amount of NaH, NaOH and SiO 2 used.

実施例７
ＮａＨとＮａＯＨのモル比１：１混合物に、ＮａＨ１００モルに対して３モルの割合でTiCl3を添加し、この混合物をボールミルに入れ、回転速度300rpm、回転時間10分間、停止
時間10分間の繰り返し条件で３時間混合した。 Example 7
TiCl 3 was added to a 1: 1 mixture of NaH and NaOH at a ratio of 3 moles with respect to 100 moles of NaH, and this mixture was placed in a ball mill. The rotation speed was 300 rpm, the rotation time was 10 minutes, and the stop time was 10 minutes. The mixture was mixed for 3 hours.

このように調製した試料275 mgを容積2.3 mlの試料セルに入れ、水素吸収・放出量測定装置に接続した。340℃でポンブ(約１３．３Ｐａ)を用いて３時間排気したのち、150℃で4.0 MPaの水素を導入した。3時間後に、用いたＮａＨ、ＮａＯＨ及びＴｉＣｌ3の合計量
を基準として2.8wt%の水素吸収が観測された。 275 mg of the sample thus prepared was placed in a sample cell having a volume of 2.3 ml and connected to a hydrogen absorption / release amount measuring device. After evacuating using a pump (about 13.3 Pa) at 340 ° C. for 3 hours, 4.0 MPa of hydrogen was introduced at 150 ° C. After 3 hours, 2.8 wt% hydrogen absorption was observed based on the total amount of NaH, NaOH and TiCl 3 used.

実施例８
ＮａＨとＮａＯＨのモル比１：１混合物に、ＮａＨ１００モルに対して５モルの割合でＮｉを添加し、この混合物をボールミルに入れ、回転速度300rpm、回転時間10分間、停止時間10分間の繰り返し条件で３時間混合した。 Example 8
Ni was added to a 1: 1 mixture of NaH and NaOH at a ratio of 5 moles with respect to 100 moles of NaH, and this mixture was placed in a ball mill, and the conditions were repeated at a rotational speed of 300 rpm, a rotational time of 10 minutes, and a stop time of 10 minutes. For 3 hours.

このように調製した試料267 mgを容積2.3 mlの試料セルに入れ、水素吸収・放出量測定装置に接続した。340℃でポンブ(約１３．３Ｐａ)を用いて３時間排気したのち、150℃で4.0 MPaの水素を導入した。3時間後に、 用いたＮａＨ、ＮａＯＨ及びＮｉの合計量を基
準として、2.7wt%の水素吸収が観測された。 267 mg of the sample thus prepared was placed in a sample cell having a volume of 2.3 ml and connected to a hydrogen absorption / release measurement apparatus. After evacuating using a pump (about 13.3 Pa) at 340 ° C. for 3 hours, 4.0 MPa of hydrogen was introduced at 150 ° C. After 3 hours, 2.7 wt% hydrogen absorption was observed based on the total amount of NaH, NaOH and Ni used.

実施例９
実施例４において水素を再吸収させた試料について、340℃でのポンプ(約１３．３Ｐａ)
を用いた排気（３時間）と、150℃、4.0 MPaでの水素吸収（３時間）を３回繰り返した結果、吸収された水素とNa2O/SiO2混合物の合計量を基準として、それぞれの水素吸収量は2.9, 2.8, 2.9 wt%であった。 Example 9
For the sample in which hydrogen was reabsorbed in Example 4, the pump at 340 ° C. (about 13.3 Pa)
As a result of repeated exhaust (3 hours) using hydrogen and hydrogen absorption (3 hours) at 150 ° C and 4.0 MPa three times, respectively, based on the total amount of absorbed hydrogen and Na 2 O / SiO 2 mixture The hydrogen absorption of 2.9, 2.8 and 2.9 wt%.

実施例１０
実施例６において水素を吸収させた試料について、340℃でのポンプ(約１３．３Ｐａ)を
用いた排気（３時間）と、150℃、4.0 MPaでの水素再吸収（３時間）を4回繰り返した結
果、用いたＮａＨ、ＮａＯＨ及びＳｉＯ2の合計量を基準として、それぞれの水素吸収量
は2.9, 2.8, 2.9, 2.9 wt%であった。 Example 10
For the sample in which hydrogen was absorbed in Example 6, exhaust (3 hours) using a pump (about 13.3 Pa) at 340 ° C. and hydrogen reabsorption (3 hours) at 150 ° C. and 4.0 MPa were performed four times. As a result of repetition, the hydrogen absorption amounts were 2.9, 2.8, 2.9, and 2.9 wt% based on the total amount of NaH, NaOH, and SiO 2 used.

実施例１１
実施例７において水素を吸収させた試料について、340℃でのポンプ(約１３．３Ｐａ)を
用いた排気（３時間）と、150℃、4.0 MPaでの水素再吸収（３時間）を4回繰り返した結
果、用いたＮａＨ、ＮａＯＨ及びＳｉＯ2の合計量を基準として、それぞれの水素吸収量
は2.8, 2.7, 2.8, 2.7 wt%であった。 Example 11
For the sample in which hydrogen was absorbed in Example 7, exhaust (3 hours) using a pump (approximately 13.3 Pa) at 340 ° C. and hydrogen reabsorption (3 hours) at 150 ° C. and 4.0 MPa were performed four times. As a result of repetition, the respective hydrogen absorption amounts were 2.8, 2.7, 2.8, and 2.7 wt% based on the total amount of NaH, NaOH, and SiO 2 used.

本発明の水素貯蔵材料の有効成分であるＮａ2Ｏ及びその水素貯蔵過程における生成物の粉末Ｘ線回折（ＸＲＤ）パターン。Powder X-ray diffraction (XRD) pattern of the product in Na 2 O and its hydrogen storage process is the active ingredient of the hydrogen storage material of the present invention. ＮａＨとＮａＯＨのモル比１：１混合物の熱重量測定（ＴＧ）の結果を示すグラフ。The graph which shows the result of the thermogravimetry (TG) of the molar ratio 1: 1 mixture of NaH and NaOH. 質量分析（ＭＳ）−ＴＰＤ(Temperature Programmed Desorption)法による脱水素測定の結果を示すグラフ。The graph which shows the result of the dehydrogenation measurement by mass spectrometry (MS) -TPD (Temperature Programmed Desorption) method.

Claims (7)

Ｎａ2Ｏを有効成分として含有することを特徴とする水素貯蔵材料（但し、ホウ素酸化物
及びその誘導体からなる群から選ばれた少なくとも一種の化合物を含む水素吸蔵材料を除く）。 A hydrogen storage material containing Na 2 O as an active ingredient (however, boron oxide)
And a hydrogen storage material containing at least one compound selected from the group consisting of derivatives thereof) . 更に、ＮａＨとＮａＯＨを含有する請求項１に記載の水素貯蔵材料。 The hydrogen storage material according to claim 1, further comprising NaH and NaOH. 更に、Ｓｉ、Ｔｉ、Ｚｒ、Ｆｅ、Ｎｉ、Ｃｒ及びこれらの元素を含有する化合物からなる群から選ばれた少なくとも一種の成分を含有する請求項１又は２に記載の水素貯蔵材料。 The hydrogen storage material according to claim 1 or 2, further comprising at least one component selected from the group consisting of Si, Ti, Zr, Fe, Ni, Cr, and compounds containing these elements. 請求項１〜３のいずれかに記載の水素貯蔵材料を水素と接触させることを特徴とする水素貯蔵方法。 A hydrogen storage method comprising contacting the hydrogen storage material according to any one of claims 1 to 3 with hydrogen. −５０℃以上、５００℃未満の温度範囲、１．３Ｐａ〜５０ＭＰａの水素圧力下で、水素貯蔵材料と水素とを接触させることを特徴とする請求項４に記載の水素貯蔵方法。 The hydrogen storage method according to claim 4, wherein the hydrogen storage material and hydrogen are brought into contact with each other under a temperature range of −50 ° C. or more and less than 500 ° C. and a hydrogen pressure of 1.3 Pa to 50 MPa. 請求項１〜３のいずれかに記載の水素貯蔵材料を水素と接触させて該水素貯蔵材料に水素を吸収させることによる水素貯蔵と、この反応によって形成されるＮａＨとＮａＯＨから水素を発生させることによる水素放出を可逆的に行うことを特徴とする水素の貯蔵及び放出方法。 Hydrogen storage by bringing the hydrogen storage material according to any one of claims 1 to 3 into contact with hydrogen and allowing the hydrogen storage material to absorb hydrogen, and generating hydrogen from NaH and NaOH formed by the reaction A method for storing and releasing hydrogen, characterized in that hydrogen release by reversible is performed reversibly. 水素貯蔵材料への水素吸収反応を、１．３Ｐａ〜５０ＭＰａの水素圧下において、−５０℃以上５００℃未満の温度範囲で行い、水素放出反応を水素吸収反応より高い温度条件下及び／又は低い水素圧下で行う請求項６に記載の水素の貯蔵及び放出方法。 The hydrogen absorption reaction to the hydrogen storage material is performed in a temperature range of −50 ° C. or more and less than 500 ° C. under a hydrogen pressure of 1.3 Pa to 50 MPa, and the hydrogen release reaction is performed under higher temperature conditions and / or lower hydrogen than the hydrogen absorption reaction. The method for storing and releasing hydrogen according to claim 6 performed under pressure.
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