JP2005305394A - Hydrogen occlusion material - Google Patents
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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
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Abstract
Description
本発明は、可逆的に水素を吸蔵、放出することのできる水素吸蔵材料に関する。 The present invention relates to a hydrogen storage material capable of reversibly storing and releasing hydrogen.
近年、二酸化炭素の排出による地球の温暖化等の環境問題や、石油資源の枯渇等のエネルギー問題から、クリーンな代替エネルギーとして水素エネルギーが注目されている。水素エネルギーの実用化にむけて、水素を安全に貯蔵、輸送する技術の開発が重要となる。水素を貯蔵できる水素吸蔵材料として、活性炭、フラーレン、ナノチューブ等の炭素材料や、水素吸蔵合金等の開発が進められている。 In recent years, hydrogen energy has attracted attention as a clean alternative energy due to environmental problems such as global warming caused by carbon dioxide emissions and energy problems such as exhaustion of petroleum resources. For the practical application of hydrogen energy, it is important to develop technology for safely storing and transporting hydrogen. As hydrogen storage materials capable of storing hydrogen, development of carbon materials such as activated carbon, fullerene, and nanotubes, and hydrogen storage alloys has been underway.
室温付近で水素を吸蔵、放出することができる実用的な水素吸蔵合金として、例えば、ＬａＮｉ5、ＴｉＦｅ等が知られている（例えば、非特許文献１参照。）。また、最も軽い元素という理由から、リチウム（Ｌｉ）を構成元素とした水素吸蔵材料の開発も試みられている（例えば、特許文献１参照。）。
上記ＬａＮｉ5、ＴｉＦｅは、Ｌａ、Ｎｉ、Ｔｉといった希少な金属を含んでいるため、その資源の確保が困難であり、コストも高い。また、水素吸蔵合金自体が重いため、単位重量当たりの水素吸蔵量は２ｗｔ％以下にとどまる。さらに、ＴｉＦｅについては、初期の水素化が難しく、水素を吸蔵、放出させるためには、予め高温、高圧下での活性化処理が必要となる。一方、Ｌｉを構成元素とした水素吸蔵材料については、水素吸蔵、放出特性が未だ満足できるレベルではなく、実用化に向けたさらなる研究開発が必要である。 Since LaNi 5 and TiFe contain rare metals such as La, Ni, and Ti, it is difficult to secure the resources and the cost is high. Further, since the hydrogen storage alloy itself is heavy, the hydrogen storage amount per unit weight is limited to 2 wt% or less. Furthermore, TiFe is difficult to hydrogenate in the initial stage, and in order to occlude and release hydrogen, activation treatment under high temperature and high pressure is required in advance. On the other hand, hydrogen storage materials containing Li as a constituent element are not yet satisfactory in hydrogen storage and release characteristics, and further research and development for practical use is necessary.
本発明は、このような実状に鑑みてなされたものであり、Ｌｉを構成元素とした実用性の高い水素吸蔵材料を提供することを課題とする。 The present invention has been made in view of such a situation, and an object thereof is to provide a highly practical hydrogen storage material using Li as a constituent element.
（１）本発明の水素吸蔵材料は、組成式Ｌｉ1-x-yＳｉxＭy（Ｍは、Ｂｅ、Ｂ、Ｃ、Ｎ、Ｎａ、Ｍｇ、Ａｌ、Ｐ、Ｋ、Ｃａ、Ｇａ、Ｇｅ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｇ、Ｐｄ、Ｙ、Ｚｒ、Ｎｂ、希土類元素から選ばれる少なくとも一種、０＜ｘ＜１、０≦ｙ＜１）で表されることを特徴とする。 (1) hydrogen storage material of the present invention, the composition formula Li 1-xy Si x M y (M is, Be, B, C, N , Na, Mg, Al, P, K, Ca, Ga, Ge, Ti , V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Pd, Y, Zr, Nb, at least one selected from rare earth elements, 0 <x <1, 0 ≦ y <1) It is characterized by that.
本発明の水素吸蔵材料は、Ｌｉ、Ｓｉを基本構成元素とする。Ｌｉ、Ｓｉは、資源が豊富で比較的安価な材料である。また、Ｌｉは最も軽量であり、Ｓｉも比較的軽量である。したがって、Ｌｉ、Ｓｉを基本構成元素とする本発明の水素吸蔵材料は、軽量かつ安価な材料となる。このため、単位重量当たりの水素吸蔵量は大きくなる。 The hydrogen storage material of the present invention uses Li and Si as basic constituent elements. Li and Si are materials that are rich in resources and relatively inexpensive. Li is the lightest and Si is relatively light. Therefore, the hydrogen storage material of the present invention having Li and Si as basic constituent elements is a lightweight and inexpensive material. For this reason, the hydrogen storage amount per unit weight becomes large.
本発明の水素吸蔵材料において、Ｌｉは、水素と反応し易い親水素性の元素であり、Ｓｉは、水素と反応し難い疎水素性の元素である。よって、ＬｉとＳｉとを合金化することで、水素化物を不安定化させ、実用的な温度範囲での水素の吸蔵、放出が可能となる。また、必要に応じて添加される添加元素Ｍは、その役割により、以下の二つのグループに分けられる。一つは、水素化物中の水素を不安定化させるグループであり、もう一つは、水素との反応速度が大きく、水素吸蔵材料を活性化させるグループである。具体的には、前者の元素は、Ｂｅ、Ｂ、Ｃ、Ｎ、Ｎａ、Ｍｇ、Ａｌ、Ｐ、Ｋ、Ｃａ、Ｇａ、Ｇｅである。また、後者の元素は、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｇ、Ｐｄ、Ｙ、Ｚｒ、Ｎｂ、希土類元素である。 In the hydrogen storage material of the present invention, Li is a hydrophilic element that easily reacts with hydrogen, and Si is a hydrophobic element that hardly reacts with hydrogen. Therefore, by alloying Li and Si, the hydride is destabilized, and hydrogen can be stored and released within a practical temperature range. Further, the additive element M added as necessary is divided into the following two groups depending on its role. One is a group that destabilizes hydrogen in a hydride, and the other is a group that has a high reaction rate with hydrogen and activates a hydrogen storage material. Specifically, the former elements are Be, B, C, N, Na, Mg, Al, P, K, Ca, Ga, and Ge. The latter elements are Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Pd, Y, Zr, Nb, and rare earth elements.
前者の元素を含有することで、水素放出温度を低下させることができる。また、後者の元素を含有することで、水素吸蔵、放出速度を向上させることができる。このように、本発明の水素吸蔵材料では、Ｓｉの含有割合、および添加元素Ｍの種類や添加割合を調整することにより、水素の吸蔵、放出温度（動作温度）や、水素の吸蔵、放出量を容易に調整することができる。そして、好適な組成とすることで、動作温度を低くすることができ、水素吸蔵量を大きくすることができる。 By containing the former element, the hydrogen release temperature can be lowered. Further, by containing the latter element, it is possible to improve the hydrogen storage and release rates. As described above, in the hydrogen storage material of the present invention, by adjusting the content ratio of Si and the type and addition ratio of the additive element M, the storage and release temperature (operating temperature) of hydrogen, and the storage and release amount of hydrogen. Can be adjusted easily. And by setting it as a suitable composition, operating temperature can be lowered | hung and hydrogen storage amount can be enlarged.
（２）本発明の水素吸蔵材料の化合物相調整方法は、上記本発明の水素吸蔵材料に対して、室温〜４００℃の温度下で水素を吸蔵、放出させる水素吸蔵放出処理を行うことで、該水素吸蔵材料に含まれる特定の化合物相の体積割合を調整することを特徴とする。 (2) The method for adjusting the compound phase of the hydrogen storage material of the present invention includes performing hydrogen storage / release treatment for storing and releasing hydrogen at a temperature of room temperature to 400 ° C. with respect to the hydrogen storage material of the present invention. The volume ratio of the specific compound phase contained in the hydrogen storage material is adjusted.
一般に、水素吸蔵材料では、水素吸蔵能の高い化合物相の体積割合が大きい方が望ましい。特定の化合物相の体積割合を変化させる方法として、熱処理法が知られている。熱処理法は、温度による化合物相の安定性の違いを利用した方法である。すなわち、水素吸蔵材料を、ある化合物相が安定であり、それ以外の化合物相が不安定である温度下に長時間保持して、安定な化合物相の体積割合を増加させる。従来では、水素吸蔵材料を８００℃以上の高温下で、数十時間保持することにより、水素吸蔵能の高い化合物相の体積割合を増加させていた。 Generally, in the hydrogen storage material, it is desirable that the volume ratio of the compound phase having a high hydrogen storage capacity is large. As a method of changing the volume ratio of a specific compound phase, a heat treatment method is known. The heat treatment method is a method using the difference in stability of the compound phase depending on the temperature. That is, the hydrogen storage material is maintained for a long time at a temperature at which a certain compound phase is stable and the other compound phases are unstable, thereby increasing the volume ratio of the stable compound phase. Conventionally, the volume ratio of the compound phase having a high hydrogen storage capacity has been increased by holding the hydrogen storage material at a high temperature of 800 ° C. or higher for several tens of hours.
本発明の水素吸蔵材料は、上述したように、比較的低温下で水素を吸蔵、放出することが可能である。この特性を利用して、本発明者は、本発明の水素吸蔵材料に含まれる化合物相の体積割合の調整を試みた。その結果、室温〜４００℃という比較的低温下で水素を吸蔵、放出させることで、特定の化合物相の体積割合が変化するという知見を得た。本発明の水素吸蔵材料では、水素の吸蔵により特定の化合物相が微結晶化し、原子が相互拡散し易くなると考えられる。このため、本発明の化合物相調整方法によれば、例えば、水素吸蔵能の高い化合物相の体積割合を、低温下で短時間に増加させることができる。さらには、水素吸蔵材料を、特定の化合物相のみで構成することもできる。 As described above, the hydrogen storage material of the present invention can store and release hydrogen at a relatively low temperature. Using this characteristic, the present inventor tried to adjust the volume ratio of the compound phase contained in the hydrogen storage material of the present invention. As a result, it has been found that the volume ratio of a specific compound phase is changed by inserting and extracting hydrogen at a relatively low temperature of room temperature to 400 ° C. In the hydrogen storage material of the present invention, it is considered that a specific compound phase is microcrystallized due to the storage of hydrogen, and atoms easily diffuse. For this reason, according to the compound phase adjustment method of the present invention, for example, the volume ratio of the compound phase having a high hydrogen storage capacity can be increased in a short time at a low temperature. Furthermore, the hydrogen storage material can be composed of only a specific compound phase.
本発明の水素吸蔵材料は、組成式Ｌｉ1-x-yＳｉxＭy（Ｍは、Ｂｅ、Ｂ、Ｃ、Ｎ、Ｎａ、Ｍｇ、Ａｌ、Ｐ、Ｋ、Ｃａ、Ｇａ、Ｇｅ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｇ、Ｐｄ、Ｙ、Ｚｒ、Ｎｂ、希土類元素から選ばれる少なくとも一種、０＜ｘ＜１、０≦ｙ＜１）で表される。Ｌｉ、Ｓｉを基本構成元素とするため、軽量かつ安価である。また、Ｓｉの含有割合および添加元素Ｍの種類や添加割合を調整することにより、動作温度を低くすることができ、水素吸蔵量を大きくすることができる。 Hydrogen storage material of the present invention, the composition formula Li 1-xy Si x M y (M is, Be, B, C, N , Na, Mg, Al, P, K, Ca, Ga, Ge, Ti, V, At least one selected from Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Pd, Y, Zr, Nb, and a rare earth element, 0 <x <1, 0 ≦ y <1). Since Li and Si are the basic constituent elements, they are lightweight and inexpensive. Further, by adjusting the Si content ratio and the type and addition ratio of the additive element M, the operating temperature can be lowered and the hydrogen storage amount can be increased.
以下、本発明の水素吸蔵材料、および水素吸蔵材料の化合物相調整方法について詳細に説明する。なお、本発明の水素吸蔵材料および水素吸蔵材料の化合物相調整方法は、下記の実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において、当業者が行い得る変更、改良等を施した種々の形態にて実施することができる。 Hereinafter, the hydrogen storage material of the present invention and the compound phase adjustment method of the hydrogen storage material will be described in detail. Note that the hydrogen storage material and the method for adjusting the compound phase of the hydrogen storage material of the present invention are not limited to the following embodiments, and modifications and improvements that can be made by those skilled in the art without departing from the scope of the present invention. It can implement with the various form which gave.
〈水素吸蔵材料〉
本発明の水素吸蔵材料は、組成式Ｌｉ1-x-yＳｉxＭyで表される。Ｓｉの含有割合ｘが大きくなると、水素吸蔵量は小さくなる。よって、Ｓｉの含有割合ｘは、水素吸蔵量を考慮して決定すればよい。例えば、実用的な水素吸蔵量を確保するためには、Ｓｉの含有割合ｘの範囲を０＜ｘ≦０．４とするとよい。また、添加元素Ｍの割合ｙは、本水素吸蔵材料の動作温度、水素吸蔵、放出量に影響する。よって、使用する添加元素Ｍの種類により、動作温度、水素吸蔵、放出量を適宜考慮して、添加元素Ｍの割合ｙを決定すればよい。例えば、水素吸蔵量を考慮して、Ｓｉの含有割合ｘを０＜ｘ≦０．４とした場合には、添加元素Ｍの割合ｙを０≦ｙ≦０．３３とすればよい。
<Hydrogen storage material>
Hydrogen storage material of the present invention is represented by the composition formula Li 1-xy Si x M y . As the Si content ratio x increases, the hydrogen storage amount decreases. Therefore, the Si content ratio x may be determined in consideration of the hydrogen storage amount. For example, in order to ensure a practical hydrogen storage amount, the range of the Si content ratio x is preferably 0 <x ≦ 0.4. Further, the ratio y of the additive element M affects the operating temperature, hydrogen storage, and release amount of the present hydrogen storage material. Therefore, the proportion y of the additive element M may be determined depending on the type of additive element M to be used, taking into account the operating temperature, hydrogen storage and release amount as appropriate. For example, in consideration of the hydrogen storage amount, when the Si content ratio x is 0 <x ≦ 0.4, the additive element M ratio y may be 0 ≦ y ≦ 0.33.
上述したように、添加元素Ｍは、その役割により二つのグループに分けられる。例えば、水素化物の水素を不安定化させ、水素放出温度を低下させるという観点では、添加元素Ｍとして、Ｂｅ、Ｂ、Ｃ、Ｎ、Ｎａ、Ｍｇ、Ａｌ、Ｐ、Ｋ、Ｃａ、Ｇａ、Ｇｅから選ばれる一種以上を用いればよい。特に、Ａｌ、Ｇｅ、Ｍｇ等が好適である。また、水素吸蔵材料を活性化させ、水素吸蔵、放出速度を向上させるという観点では、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｇ、Ｐｄ、Ｙ、Ｚｒ、Ｎｂ、希土類元素から選ばれる一種以上を用いればよい。特に、Ｚｎ、Ａｇ、Ｖ等が好適である。 As described above, the additive element M is divided into two groups depending on its role. For example, from the viewpoint of destabilizing hydrogen in the hydride and lowering the hydrogen release temperature, the additive element M is Be, B, C, N, Na, Mg, Al, P, K, Ca, Ga, Ge. One or more selected from the above may be used. In particular, Al, Ge, Mg, etc. are suitable. Further, from the viewpoint of activating the hydrogen storage material and improving the hydrogen storage and release rate, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Pd, Y, Zr, Nb, One or more selected from rare earth elements may be used. In particular, Zn, Ag, V and the like are suitable.
本発明の水素吸蔵材料の一実施形態として、Ｌｉ1-xＳｉx（０＜ｘ＜１）が挙げられる（上記組成式中ｙ＝０に相当。）。Ｌｉ1-xＳｉxは、軽量かつ安価なＬｉ、Ｓｉのみから構成されるため、単位重量当たりの水素吸蔵量が大きく、安価で製造し易いという利点を有する。この場合、水素吸蔵量をより大きくするという理由から、Ｓｉの含有割合ｘの範囲を０＜ｘ＜０．５とするとよい。０＜ｘ＜０．３６とするとより好適である。 One embodiment of the hydrogen storage material of the present invention is Li 1-x Si x (0 <x <1) (corresponding to y = 0 in the above composition formula). Since Li 1-x Si x is composed only of light and inexpensive Li and Si, it has an advantage that it has a large hydrogen storage amount per unit weight, is inexpensive and easy to manufacture. In this case, the range of the Si content ratio x is preferably 0 <x <0.5 because the hydrogen storage amount is increased. It is more preferable that 0 <x <0.36.
本発明の水素吸蔵材料の製造方法は、特に限定されるものではない。例えば、アーク溶解法、高周波誘導加熱溶解法等の通常の合金の製造方法により製造することができる。例えば、上記溶解法では、Ｌｉ粒、Ｓｉ粉末、必要に応じて添加元素Ｍの粉末を目的の組成となるよう秤量、混合した後、溶解して凝固させればよい。溶解法によれば、メカニカルミリング等の機械的処理法と比較して、本発明の水素吸蔵材料を容易に低コストで製造することができる。 The method for producing the hydrogen storage material of the present invention is not particularly limited. For example, it can be manufactured by a normal alloy manufacturing method such as an arc melting method or a high frequency induction heating melting method. For example, in the above melting method, Li particles, Si powder, and if necessary, powder of additive element M may be weighed and mixed so as to have a target composition, and then dissolved and solidified. According to the melting method, the hydrogen storage material of the present invention can be easily produced at low cost as compared with a mechanical processing method such as mechanical milling.
〈水素吸蔵材料の化合物相調整方法〉
本発明の水素吸蔵材料の化合物相調整方法は、上記本発明の水素吸蔵材料に対して、室温〜４００℃の温度下で水素を吸蔵、放出させる水素吸蔵放出処理を行うことで、該水素吸蔵材料に含まれる特定の化合物相の体積割合を調整する。
<Method of adjusting compound phase of hydrogen storage material>
The method for adjusting the compound phase of the hydrogen storage material of the present invention comprises performing a hydrogen storage / release treatment for storing and releasing hydrogen at a temperature of room temperature to 400 ° C. with respect to the hydrogen storage material of the present invention. The volume ratio of the specific compound phase contained in the material is adjusted.
水素吸蔵放出処理は、室温〜４００℃の温度下で行う。水素吸蔵材料により、水素の吸蔵、放出に最適な温度を適宜採用すればよい。そして、水素吸蔵材料に、所定の温度、水素圧力下で水素を吸蔵させ、その後、水素を排気し、所定の温度下で水素を放出させる。水素を吸蔵させる際の水素圧力は、１〜１０ＭＰａとすればよい。また、水素の吸蔵、放出は、それぞれ１〜５時間程度行えばよい。この水素吸蔵放出処理により、特定の化合物相の体積割合が変化する。 The hydrogen storage / release treatment is performed at a temperature of room temperature to 400 ° C. What is necessary is just to employ | adopt suitably the optimal temperature for occlusion and discharge | release of hydrogen with a hydrogen storage material. Then, the hydrogen storage material is allowed to store hydrogen under a predetermined temperature and hydrogen pressure, and then the hydrogen is exhausted and released under a predetermined temperature. The hydrogen pressure at the time of occlusion of hydrogen may be 1 to 10 MPa. In addition, hydrogen storage and release may be performed for about 1 to 5 hours, respectively. By this hydrogen storage / release treatment, the volume ratio of the specific compound phase changes.
体積割合を調整する化合物相の好適な態様として、例えば、Ｇｅ2Ｏｓ型結晶構造を有する化合物相が挙げられる。この化合物相は、水素吸蔵能が高い。よって、その体積割合を増加させることにより、本発明の水素吸蔵材料の水素吸蔵、放出能をより向上させることができる。 As a preferred embodiment of the compound phase adjusting the volume ratio, for example, a compound phase having a Ge 2 Os-type crystal structure. This compound phase has a high hydrogen storage capacity. Therefore, by increasing the volume ratio, the hydrogen storage / release capability of the hydrogen storage material of the present invention can be further improved.
上記実施形態に基づいて、本発明の水素吸蔵材料を種々製造した。そして、製造した水素吸蔵材料に、所定の条件下で水素を吸蔵させ、それらの水素吸蔵能を評価した。また、水素吸蔵放出処理を行い、特定の化合物相の体積割合の変化を調査した。以下、製造した水素吸蔵材料ごとに説明する。 Based on the above embodiment, various hydrogen storage materials of the present invention were produced. And the produced hydrogen storage material was made to occlude hydrogen on predetermined conditions, and those hydrogen occlusion ability was evaluated. In addition, hydrogen storage / release treatment was performed, and changes in the volume ratio of specific compound phases were investigated. Hereinafter, each manufactured hydrogen storage material will be described.
（１）Ｌｉ0.65Ｓｉ0.35
（ａ）Ｌｉ0.65Ｓｉ0.35の製造
Ｌｉ粒（純度９９％以上）とＳｉ粉末（純度９９．９９９％）とを、目的とする組成となるよう秤量、混合した後、金型に入れ、アルゴンガス雰囲気の加熱炉にて加熱、溶解した。自然冷却した後、得られたインゴットをアルゴンガスで満たされたグローブボックス内で粉砕し、粉末状のＬｉ0.65Ｓｉ0.35を得た。得られたＬｉ0.65Ｓｉ0.35について、ＣｕΚα線を用いた粉末法によるＸ線回折測定を行った。Ｘ線回折プロファイルから、得られたＬｉ0.65Ｓｉ0.35は、Ｌｉ2Ｓｉ相（Ｇｅ2Ｏｓ型結晶構造）と、Ｌｉ12Ｓｉ7相（Ｌｉ12Ｓｉ7型結晶構造）との混相であることを確認した。
(1) Li 0.65 Si 0.35
(A) Production of Li 0.65 Si 0.35 Li particles (purity 99% or more) and Si powder (purity 99.999%) were weighed and mixed to achieve the desired composition, then placed in a mold, and argon gas It heated and melt | dissolved in the heating furnace of atmosphere. After natural cooling, the obtained ingot was pulverized in a glove box filled with argon gas to obtain powdery Li 0.65 Si 0.35 . The obtained Li 0.65 Si 0.35 was subjected to X-ray diffraction measurement by a powder method using CuΚα rays. From the X-ray diffraction profile, the obtained Li 0.65 Si 0.35 is a mixed phase of Li 2 Si phase (Ge 2 Os type crystal structure) and Li 12 Si 7 phase (Li 12 Si 7 type crystal structure). confirmed.
（ｂ）水素吸蔵能の評価
製造したＬｉ0.65Ｓｉ0.35を、水素加圧チャンバーに入れ、温度３００℃、水素圧力９ＭＰａの条件で水素を吸蔵させた。吸蔵された水素量は、圧力−組成等温線（ＰＣＴ線）を求めるジーベルツ法により測定した（ＪＩＳ Ｈ ７２０１−１９９１、以下同様。）。水素の吸蔵開始から約５時間経過後の水素吸蔵量は、約２ｗｔ％となった。また、水素吸蔵後に、Ｘ線回折プロファイルが変化することを確認した。
(B) Evaluation of hydrogen storage capacity The produced Li 0.65 Si 0.35 was put in a hydrogen pressure chamber, and hydrogen was stored under conditions of a temperature of 300 ° C. and a hydrogen pressure of 9 MPa. The amount of hydrogen occluded was measured by the Siebelz method for obtaining a pressure-composition isotherm (PCT line) (JIS H 7201-1991, the same applies hereinafter). The hydrogen storage amount after about 5 hours from the start of hydrogen storage was about 2 wt%. It was also confirmed that the X-ray diffraction profile changed after hydrogen storage.
（２）Ｌｉ0.82Ｓｉ0.18
（ａ）Ｌｉ0.82Ｓｉ0.18の製造
Ｌｉ粒（純度９９％以上）とＳｉ粉末（純度９９．９９９％）とを、目的とする組成となるよう秤量、混合した後、金型に入れ、アルゴンガス雰囲気の加熱炉にて加熱、溶解した。自然冷却した後、得られたインゴットをアルゴンガスで満たされたグローブボックス内で粉砕し、粉末状のＬｉ0.82Ｓｉ0.18を得た。得られたＬｉ0.82Ｓｉ0.18について、上記同様にＸ線回折測定を行った。Ｘ線回折プロファイルから、得られたＬｉ0.82Ｓｉ0.18は、Ｌｉ22Ｓｉ5相（Ｌｉ22Ｐｂ5型結晶構造）を主相とすることを確認した。
(2) Li 0.82 Si 0.18
(A) Production of Li 0.82 Si 0.18 Li particles (purity 99% or more) and Si powder (purity 99.999%) were weighed and mixed to achieve the desired composition, then placed in a mold, and argon gas It heated and melt | dissolved in the heating furnace of atmosphere. After natural cooling, the obtained ingot was pulverized in a glove box filled with argon gas to obtain powdered Li 0.82 Si 0.18 . X-ray diffraction measurement was performed on the obtained Li 0.82 Si 0.18 in the same manner as described above. From the X-ray diffraction profile, it was confirmed that the obtained Li 0.82 Si 0.18 has a Li 22 Si 5 phase (Li 22 Pb 5 type crystal structure) as a main phase.
（ｂ）水素吸蔵能の評価
製造したＬｉ0.82Ｓｉ0.18を、水素加圧チャンバーに入れ、温度３５０℃、水素圧力９ＭＰａの条件で水素を吸蔵させた。水素の吸蔵開始から約５時間経過後の水素吸蔵量は、約３．２ｗｔ％となった。また、水素吸蔵後に、Ｘ線回折プロファイルが変化することを確認した。
(B) Evaluation of hydrogen storage capacity The produced Li 0.82 Si 0.18 was placed in a hydrogen pressure chamber, and hydrogen was stored under conditions of a temperature of 350 ° C. and a hydrogen pressure of 9 MPa. The hydrogen storage amount after about 5 hours from the start of hydrogen storage was about 3.2 wt%. It was also confirmed that the X-ray diffraction profile changed after hydrogen storage.
（３）Ｌｉ0.63Ｓｉ0.21Ａｌ0.16
（ａ）Ｌｉ0.63Ｓｉ0.21Ａｌ0.16の製造
Ｌｉ粒（純度９９％以上）とＳｉ粉末（純度９９．９９９％）と、Ａｌ粉末（純度９９．９９％）とを、目的とする組成となるよう秤量、混合した後、アルゴンガス雰囲気にて高周波溶解した。自然冷却した後、得られたインゴットをアルゴンガスで満たされたグローブボックス内で粉砕し、粉末状のＬｉ0.63Ｓｉ0.21Ａｌ0.16を得た。得られたＬｉ0.63Ｓｉ0.21Ａｌ0.16について、上記同様にＸ線回折測定を行った。
(3) Li 0.63 Si 0.21 Al 0.16
(A) Production of Li 0.63 Si 0.21 Al 0.16 Li grains (purity 99% or more), Si powder (purity 99.999%), and Al powder (purity 99.99%) so as to have the intended composition After weighing and mixing, high-frequency dissolution was performed in an argon gas atmosphere. After natural cooling, the obtained ingot was pulverized in a glove box filled with argon gas to obtain powdered Li 0.63 Si 0.21 Al 0.16 . X-ray diffraction measurement was performed on the obtained Li 0.63 Si 0.21 Al 0.16 in the same manner as described above.
（ｂ）水素吸蔵能の評価
製造したＬｉ0.63Ｓｉ0.21Ａｌ0.16を、水素加圧チャンバーに入れ、温度３５０℃、水素圧力９ＭＰａの条件で水素を吸蔵させた。水素の吸蔵開始から約４時間経過後の水素吸蔵量は、約３ｗｔ％となった。また、水素吸蔵後に、Ｘ線回折プロファイルが変化することを確認した。
(B) Evaluation of hydrogen storage capacity The produced Li 0.63 Si 0.21 Al 0.16 was placed in a hydrogen pressure chamber, and hydrogen was stored under conditions of a temperature of 350 ° C. and a hydrogen pressure of 9 MPa. The hydrogen storage amount after about 4 hours from the start of hydrogen storage was about 3 wt%. It was also confirmed that the X-ray diffraction profile changed after hydrogen storage.
（４）Ｌｉ0.5Ｓｉ0.25Ｚｎ0.25
（ａ）Ｌｉ0.5Ｓｉ0.25Ｚｎ0.25の製造
Ｌｉ粒（純度９９％以上）とＳｉ粉末（純度９９．９９９％）と、Ｚｎ粉末（純度９９．９９％）とを、目的とする組成となるよう秤量、混合した後、アルゴンガス雰囲気にて高周波溶解した。自然冷却した後、得られたインゴットをアルゴンガスで満たされたグローブボックス内で粉砕し、粉末状のＬｉ0.5Ｓｉ0.25Ｚｎ0.25を得た。得られたＬｉ0.5Ｓｉ0.25Ｚｎ0.25について、上記同様にＸ線回折測定を行った。
(4) Li 0.5 Si 0.25 Zn 0.25
(A) Production of Li 0.5 Si 0.25 Zn 0.25 Li grains (purity 99% or more), Si powder (purity 99.999%), and Zn powder (purity 99.99%) so as to have the intended composition After weighing and mixing, high-frequency dissolution was performed in an argon gas atmosphere. After natural cooling, the obtained ingot was pulverized in a glove box filled with argon gas to obtain powdered Li 0.5 Si 0.25 Zn 0.25 . The obtained Li 0.5 Si 0.25 Zn 0.25 was subjected to X-ray diffraction measurement in the same manner as described above.
（ｂ）水素吸蔵能の評価
製造したＬｉ0.5Ｓｉ0.25Ｚｎ0.25を、水素加圧チャンバーに入れ、温度３５０℃、水素圧力９ＭＰａの条件で水素を吸蔵させた。水素の吸蔵開始から約４時間経過後の水素吸蔵量は、約１ｗｔ％となった。また、水素吸蔵後に、Ｘ線回折プロファイルが変化することを確認した。
(B) Evaluation of hydrogen storage capacity The produced Li 0.5 Si 0.25 Zn 0.25 was placed in a hydrogen pressurization chamber, and hydrogen was stored under conditions of a temperature of 350 ° C. and a hydrogen pressure of 9 MPa. The hydrogen storage amount after about 4 hours from the start of hydrogen storage was about 1 wt%. It was also confirmed that the X-ray diffraction profile changed after hydrogen storage.
（ｃ）水素吸蔵放出処理による化合物相の体積割合の調整
製造したＬｉ0.5Ｓｉ0.25Ｚｎ0.25を、水素加圧チャンバーに入れ、温度３５０℃、水素圧力９ＭＰａの条件で、３時間水素を吸蔵させた。その後、３５０℃の温度下で、ロータリーポンプによる真空排気を３時間行い、水素を放出させた。
(C) Adjustment of the volume ratio of the compound phase by hydrogen storage / release treatment The produced Li 0.5 Si 0.25 Zn 0.25 was placed in a hydrogen pressure chamber, and hydrogen was stored for 3 hours under conditions of a temperature of 350 ° C. and a hydrogen pressure of 9 MPa. . Thereafter, evacuation with a rotary pump was performed for 3 hours at a temperature of 350 ° C. to release hydrogen.
この水素吸蔵放出処理後のＸ線回折プロファイルと、水素吸蔵前のＸ線回折プロファイルとから、Ｃａ2ＺｎＳｉ相の体積割合を算出した。Ｃａ2ＺｎＳｉ相の体積割合は、水素吸蔵前では約７２％であったのに対し、水素吸蔵放出処理後では約９７％となった。つまり、水素の吸蔵放出処理により、Ｃａ2ＺｎＳｉ相の体積割合が増加した。 The volume ratio of the Ca 2 ZnSi phase was calculated from the X-ray diffraction profile after this hydrogen storage / release treatment and the X-ray diffraction profile before hydrogen storage. The volume ratio of the Ca 2 ZnSi phase was about 72% before hydrogen storage, and about 97% after hydrogen storage / release treatment. That is, the volume ratio of the Ca 2 ZnSi phase was increased by the hydrogen storage / release treatment.
水素吸蔵放出処理によりＣａ2ＺｎＳｉ相の体積割合が増加したＬｉ0.5Ｓｉ0.25Ｚｎ0.25は、温度３５０℃、水素圧力９ＭＰａの条件で、約２ｗｔ％の水素を吸蔵した。 Li 0.5 Si 0.25 Zn 0.25 , in which the volume ratio of the Ca 2 ZnSi phase was increased by the hydrogen storage / release treatment, occluded about 2 wt% of hydrogen under conditions of a temperature of 350 ° C. and a hydrogen pressure of 9 MPa.
（５）Ｌｉ0.55Ｓｉ0.29Ａｌ0.16
（ａ）Ｌｉ0.55Ｓｉ0.29Ａｌ0.16の製造
Ｌｉ粒（純度９９％以上）とＳｉ粉末（純度９９．９９９％）と、Ａｌ粉末（純度９９．９９％）とを、目的とする組成となるよう秤量、混合した後、アルゴンガス雰囲気にて高周波溶解した。自然冷却した後、得られたインゴットをアルゴンガスで満たされたグローブボックス内で粉砕し、粉末状のＬｉ0.55Ｓｉ0.29Ａｌ0.16を得た。得られたＬｉ0.55Ｓｉ0.29Ａｌ0.16について、上記同様にＸ線回折測定を行った。
(5) Li 0.55 Si 0.29 Al 0.16
(A) Production of Li 0.55 Si 0.29 Al 0.16 Li grains (purity 99% or more), Si powder (purity 99.999%), and Al powder (purity 99.99%) so as to have the intended composition After weighing and mixing, high-frequency dissolution was performed in an argon gas atmosphere. After natural cooling, the obtained ingot was pulverized in a glove box filled with argon gas to obtain powdered Li 0.55 Si 0.29 Al 0.16 . X-ray diffraction measurement was performed on the obtained Li 0.55 Si 0.29 Al 0.16 in the same manner as described above.
（ｂ）水素吸蔵能の評価
製造したＬｉ0.55Ｓｉ0.29Ａｌ0.16を、水素加圧チャンバーに入れ、温度３５０℃、水素圧力９ＭＰａの条件で水素を吸蔵させた。水素の吸蔵開始から約４時間経過後の水素吸蔵量は、約２．７ｗｔ％となった。
(B) Evaluation of hydrogen storage capacity The produced Li 0.55 Si 0.29 Al 0.16 was placed in a hydrogen pressure chamber, and hydrogen was stored under conditions of a temperature of 350 ° C. and a hydrogen pressure of 9 MPa. The hydrogen storage amount after about 4 hours from the start of hydrogen storage was about 2.7 wt%.
（ｃ）水素吸蔵放出処理による化合物相の体積割合の調整
製造したＬｉ0.55Ｓｉ0.29Ａｌ0.16を、水素加圧チャンバーに入れ、温度３５０℃、水素圧力９ＭＰａの条件で、３時間水素を吸蔵させた。その後、３５０℃の温度下で、ロータリーポンプによる真空排気を３時間行い、水素を放出させた。
(C) Adjustment of volume ratio of compound phase by hydrogen storage / release treatment The manufactured Li 0.55 Si 0.29 Al 0.16 was put into a hydrogen pressure chamber, and hydrogen was stored for 3 hours under conditions of a temperature of 350 ° C. and a hydrogen pressure of 9 MPa. . Thereafter, evacuation with a rotary pump was performed for 3 hours at a temperature of 350 ° C. to release hydrogen.
この水素吸蔵放出処理後のＸ線回折プロファイルと、水素吸蔵前のＸ線回折プロファイルとから、ＬｉＡｌＳｉ相の体積割合を算出した。ＬｉＡｌＳｉ相の体積割合は、水素吸蔵前では約３０％であったのに対し、水素吸蔵放出処理後では約７０％となった。つまり、水素の吸蔵放出処理により、ＬｉＡｌＳｉ相の体積割合が増加した。 The volume ratio of the LiAlSi phase was calculated from the X-ray diffraction profile after this hydrogen storage / release treatment and the X-ray diffraction profile before hydrogen storage. The volume ratio of the LiAlSi phase was about 30% before hydrogen storage, and about 70% after hydrogen storage / release treatment. That is, the volume ratio of the LiAlSi phase was increased by the hydrogen storage / release treatment.
Claims (6)
The volume ratio of the specific compound phase contained in the hydrogen storage material by performing a hydrogen storage / release treatment for storing and releasing hydrogen at a temperature of room temperature to 400 ° C. with respect to the hydrogen storage material according to claim 1. For adjusting the compound phase of the hydrogen storage material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007270209A (en) * | 2006-03-30 | 2007-10-18 | Toshiba Corp | Hydrogen storage alloy, hydrogen storage film and hydrogen storage tank |
| JP2014047113A (en) * | 2012-08-31 | 2014-03-17 | Toyota Central R&D Labs Inc | Silicon compound, anode for lithium battery, lithium battery and method of manufacturing silicon compound |
| EP3292578A4 (en) * | 2015-05-04 | 2018-12-05 | BASF Corporation | Electrochemical hydrogen storage electrodes and cells |
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2004
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007270209A (en) * | 2006-03-30 | 2007-10-18 | Toshiba Corp | Hydrogen storage alloy, hydrogen storage film and hydrogen storage tank |
| JP2014047113A (en) * | 2012-08-31 | 2014-03-17 | Toyota Central R&D Labs Inc | Silicon compound, anode for lithium battery, lithium battery and method of manufacturing silicon compound |
| EP3292578A4 (en) * | 2015-05-04 | 2018-12-05 | BASF Corporation | Electrochemical hydrogen storage electrodes and cells |
| US10522827B2 (en) | 2015-05-04 | 2019-12-31 | Basf Corporation | Electrochemical hydrogen storage electrodes and cells |
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