JP5034895B2 - Hydrogen supply device and fuel cell system - Google Patents
Hydrogen supply device and fuel cell system Download PDFInfo
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- JP5034895B2 JP5034895B2 JP2007305248A JP2007305248A JP5034895B2 JP 5034895 B2 JP5034895 B2 JP 5034895B2 JP 2007305248 A JP2007305248 A JP 2007305248A JP 2007305248 A JP2007305248 A JP 2007305248A JP 5034895 B2 JP5034895 B2 JP 5034895B2
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y02E60/32—Hydrogen storage
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Description
本発明は、貯蔵した水素を機器へ供給する水素供給装置、及び、当該水素供給装置を備える燃料電池システムに関する。 The present invention relates to a hydrogen supply device that supplies stored hydrogen to equipment, and a fuel cell system including the hydrogen supply device.
地球温暖化対策技術として研究が進められている燃料電池は、反応物（水素や空気等）の電気化学反応の過程で生じた電気エネルギーを外部へ取り出す装置であり、有害ガス等を発生させないクリーンなエネルギー源として知られている。燃料電池を搭載した自動車（以下「燃料電池車」という。）において、反応物として水素を用いる場合、使用される水素を貯蔵する手段が必要とされ、水素の貯蔵形態としては、気体の水素を直接充填する形態や液体水素を用いる形態のほか、水素吸蔵合金を用いる形態等が提案されている。これらの中でも、液体水素よりも多量の水素を貯蔵でき、安全性に優れる等の観点から、水素吸蔵合金を用いる形態が注目されている。 The fuel cell, which is being studied as a global warming countermeasure technology, is a device that extracts the electrical energy generated during the electrochemical reaction of reactants (hydrogen, air, etc.) to the outside, and is a clean device that does not generate harmful gases. Known as a powerful energy source. In a vehicle equipped with a fuel cell (hereinafter referred to as “fuel cell vehicle”), when hydrogen is used as a reactant, a means for storing the hydrogen to be used is required. As a hydrogen storage mode, gaseous hydrogen is used. In addition to the form of direct filling and liquid hydrogen, a form of using a hydrogen storage alloy has been proposed. Among these, from the viewpoint of being able to store a larger amount of hydrogen than liquid hydrogen and being excellent in safety, a form using a hydrogen storage alloy is attracting attention.
水素吸蔵合金は、温度や圧力を制御することにより水素を吸蔵・放出し得る合金である。ここで、燃料電池車に搭載される水素貯蔵手段には、燃料電池車の航続距離を長期間に亘って維持するために、多量の水素を吸蔵可能であることが必要とされる。さらに、燃料電池車の運転状態に応じて、幅広い水素放出速度に対応可能であることが必要とされる。それゆえ、燃料電池車に搭載される水素貯蔵手段に水素吸蔵合金が収容される場合、水素吸蔵量が大きく、かつ、水素の吸蔵・放出速度が大きい水素吸蔵合金を用いることが重要になる。 A hydrogen storage alloy is an alloy that can store and release hydrogen by controlling temperature and pressure. Here, the hydrogen storage means mounted on the fuel cell vehicle is required to be able to store a large amount of hydrogen in order to maintain the cruising distance of the fuel cell vehicle over a long period of time. Furthermore, it is necessary to be able to cope with a wide range of hydrogen release rates depending on the operating state of the fuel cell vehicle. Therefore, when a hydrogen storage alloy is accommodated in the hydrogen storage means mounted on the fuel cell vehicle, it is important to use a hydrogen storage alloy having a large hydrogen storage amount and a high hydrogen storage / release rate.
水素吸蔵合金を備えた水素貯蔵手段に関する技術として、例えば、特許文献１には、熱供給部材を備えたタンク本体内に水素吸蔵合金を充填してなる水素吸蔵合金タンクにおいて、上記水素吸蔵合金を、所定の水素放出圧を得るに必要な温度であってその属性から決定される属性温度が異なる複数種類の水素吸蔵合金で構成するとともに、該複数の水素吸蔵合金を、属性温度の高い水素吸蔵合金ほど上記タンク本体内の上記熱供給部材から供給される熱量が多い部位寄りに位置せしめた状態で配置した水素吸蔵合金タンク構造が開示されている。また、特許文献２には、水素を吸蔵・解離する水素吸蔵材を備えた水素供給装置に関する技術が開示されている。
As a technique related to a hydrogen storage means provided with a hydrogen storage alloy, for example, Patent Document 1 discloses a hydrogen storage alloy tank in which a hydrogen storage alloy is filled in a tank body provided with a heat supply member. And a plurality of hydrogen storage alloys having different attribute temperatures determined from their attributes, which are necessary to obtain a predetermined hydrogen release pressure, and the plurality of hydrogen storage alloys are combined with hydrogen storage having a high attribute temperature. A hydrogen storage alloy tank structure is disclosed in which the alloy is positioned closer to a portion where the amount of heat supplied from the heat supply member in the tank body is larger in the alloy body.
特許文献１に開示されている技術によれば、水素吸蔵合金タンクに複数種類の水素吸蔵合金が備えられるので、長期間に亘って水素を放出することが可能になると考えられる。しかし、特許文献１に開示されている技術では、水素の放出速度については考慮されていない。水素吸蔵合金タンクには、水素を貯蔵可能であるのみならず、必要十分な量の水素を放出可能であることも必要とされるため、水素の放出速度について考慮されていない特許文献１に開示された技術では、例えば、一度に大量の水素が必要とされる場面において、十分な量の水素を供給できない虞があるという問題があった。かかる問題は、特許文献２に開示されている技術、及び、特許文献１に開示されている技術と特許文献２に開示されている技術とを組み合わせた技術によっても解決が困難であった。
According to the technique disclosed in Patent Document 1, it is considered that hydrogen can be released over a long period of time because a plurality of types of hydrogen storage alloys are provided in the hydrogen storage alloy tank. However, the technique disclosed in Patent Document 1 does not consider the hydrogen release rate. Since the hydrogen storage alloy tank is required not only to store hydrogen but also to be able to release a necessary and sufficient amount of hydrogen, it is disclosed in Patent Document 1 in which no consideration is given to the hydrogen release rate. For example, there is a problem that a sufficient amount of hydrogen may not be supplied in a scene where a large amount of hydrogen is required at once. Such a problem has been difficult to solve even by the technique disclosed in
そこで本発明は、水素吸蔵量は多いが水素放出速度は小さい水素貯蔵材料が備えられていても、必要とされる水素放出量を長期間に亘って確保することが可能な水素供給装置、及び、当該水素供給装置を備える燃料電池システムを提供することを課題とする。 Accordingly, the present invention provides a hydrogen supply device capable of securing a required hydrogen release amount over a long period of time even if a hydrogen storage material having a large hydrogen storage amount but a low hydrogen release rate is provided, and An object of the present invention is to provide a fuel cell system including the hydrogen supply device.
上記課題を解決するために、本発明は以下の手段をとる。すなわち、
第１の本発明は、少なくとも第１の水素貯蔵材料及び第２の水素貯蔵材料を収容した、水素貯蔵手段を具備し、第２の水素貯蔵材料の水素吸蔵圧は、第１の水素貯蔵材料の水素放出圧よりも低く、かつ、第２の水素貯蔵材料の水素放出速度は、第１の水素貯蔵材料の水素放出速度よりも大きいことを特徴とする、水素供給装置である。
In order to solve the above problems, the present invention takes the following means. That is,
1st this invention comprises the hydrogen storage means which accommodated at least the 1st hydrogen storage material and the 2nd hydrogen storage material, The hydrogen occlusion pressure of the 2nd hydrogen storage material is 1st hydrogen storage material The hydrogen supply device is characterized in that the hydrogen release pressure of the second hydrogen storage material is lower than the hydrogen release pressure of the first hydrogen storage material, and the hydrogen release rate of the second hydrogen storage material is higher than the hydrogen release rate of the first hydrogen storage material.
ここで、「第１の水素貯蔵材料」及び「第２の水素貯蔵材料」は、水素を貯蔵・放出可能な材料であれば、その形態は特に限定されるものではない。第１の水素貯蔵材料及び第２の水素貯蔵材料の具体例としては、水素吸蔵合金を挙げることができる。さらに、本発明における「水素吸蔵圧」及び「水素放出圧」は、Hydrogen pressure-composition-isotherms曲線（以下「ＰＣＴ曲線」という。）のプラトー領域における圧力（プラトー領域が水平ではなく傾きを有する直線で近似される場合には、当該プラトー領域の平均圧力（プラトー領域の最大圧力をＰｘ、最小圧力をＰｙとするとき、（Ｐｘ＋Ｐｙ）／２で表される圧力））を意味する。 Here, the form of the “first hydrogen storage material” and the “second hydrogen storage material” is not particularly limited as long as the material can store and release hydrogen. Specific examples of the first hydrogen storage material and the second hydrogen storage material include a hydrogen storage alloy. Furthermore, “hydrogen storage pressure” and “hydrogen release pressure” in the present invention are pressures in a plateau region of a hydrogen pressure-composition-isotherms curve (hereinafter referred to as “PCT curve”) (a straight line in which the plateau region has an inclination rather than horizontal) Is an average pressure of the plateau region (a pressure represented by (Px + Py) / 2 when the maximum pressure in the plateau region is Px and the minimum pressure is Py)).
上記第１の本発明において、第１の水素貯蔵材料及び第２の水素貯蔵材料が、同一容器に収容されていることが好ましい。 In the first aspect of the present invention, it is preferable that the first hydrogen storage material and the second hydrogen storage material are accommodated in the same container.
第２の本発明は、上記第１の本発明にかかる水素供給装置と、該水素供給装置から取り出された水素が供給される燃料電池と、を備えることを特徴とする、燃料電池システムである。 According to a second aspect of the present invention, there is provided a fuel cell system comprising: the hydrogen supply device according to the first aspect of the present invention; and a fuel cell to which hydrogen extracted from the hydrogen supply device is supplied. .
第１の本発明によれば、水素吸蔵量は多いが相対的に水素放出速度の小さい第１の水素貯蔵材料に加え、相対的に水素放出速度の大きい第２の水素貯蔵材料が備えられ、かつ、当該第２の水素貯蔵材料の水素貯蔵圧は、第１の水素貯蔵材料の水素放出圧よりも小さい。そのため、水素貯蔵手段内の圧力が高い間は、高圧ガスの状態で存在する水素を供給でき、水素貯蔵手段内の圧力が低下すると、第１の水素貯蔵材料及び第２の水素貯蔵材料から水素が放出される。そして、第１の水素貯蔵材料からのみでは水素の供給が追いつかない時、水素放出速度の大きい第２の水素貯蔵材料から水素が放出される。それゆえ、水素貯蔵手段内の圧力の高低によらず、水素放出速度の大きい状態を維持することができる。したがって、第１の本発明によれば、水素吸蔵量が多く、水素放出速度が小さい水素貯蔵材料が備えられていても、必要とされる水素放出量を長期間に亘って確保することが可能な、水素供給装置を提供することができる。 According to the first aspect of the present invention, in addition to the first hydrogen storage material having a large hydrogen storage amount but a relatively low hydrogen release rate, a second hydrogen storage material having a relatively high hydrogen release rate is provided. In addition, the hydrogen storage pressure of the second hydrogen storage material is smaller than the hydrogen release pressure of the first hydrogen storage material. Therefore, while the pressure in the hydrogen storage means is high, hydrogen existing in the state of high-pressure gas can be supplied. When the pressure in the hydrogen storage means decreases, the hydrogen from the first hydrogen storage material and the second hydrogen storage material Is released. Then, when hydrogen supply cannot catch up with only the first hydrogen storage material, hydrogen is released from the second hydrogen storage material having a high hydrogen release rate. Therefore, it is possible to maintain a high hydrogen release rate regardless of the pressure in the hydrogen storage means. Therefore, according to the first aspect of the present invention, even if a hydrogen storage material having a large hydrogen storage amount and a low hydrogen release rate is provided, the required hydrogen release amount can be ensured over a long period of time. In addition, a hydrogen supply device can be provided.
第１の本発明において、第１の水素貯蔵材料及び第２の水素貯蔵材料が同一容器に収容されることにより、第１の水素貯蔵材料から第２の水素貯蔵材料に水素が移動する際に、水素を吸蔵する第２の水素貯蔵材料から発せられた熱を、水素を放出する際に熱を吸収する第１の水素貯蔵材料へと移動させることができる。すなわち、かかる形態とすることで、水素の吸蔵・放出時における外部からの熱の供給が不要になるので、上記効果に加えて補機損失を低減することが可能な、水素供給装置を提供することができる。 In the first aspect of the present invention, when the first hydrogen storage material and the second hydrogen storage material are accommodated in the same container, hydrogen moves from the first hydrogen storage material to the second hydrogen storage material. The heat generated from the second hydrogen storage material that occludes hydrogen can be transferred to the first hydrogen storage material that absorbs heat when releasing hydrogen. That is, by adopting such a configuration, it is not necessary to supply heat from the outside at the time of occlusion / release of hydrogen, and thus a hydrogen supply device capable of reducing auxiliary equipment loss in addition to the above effects is provided. be able to.
第２の本発明によれば、上記第１の本発明にかかる水素供給装置が備えられるので、水素吸蔵量が多く、水素放出速度が小さい水素貯蔵材料が備えられていても、必要とされる水素放出量を長期間に亘って確保することが可能な、燃料電池システムを提供することができる。 According to the second aspect of the present invention, since the hydrogen supply device according to the first aspect of the present invention is provided, it is required even if a hydrogen storage material having a large hydrogen storage amount and a low hydrogen release rate is provided. It is possible to provide a fuel cell system capable of securing a hydrogen release amount over a long period of time.
水素貯蔵材料を用いて水素を貯蔵する場合、水素貯蔵量の多い水素貯蔵材料に貯蔵することが有効である。しかし、水素貯蔵量の多い水素貯蔵材料は、水素の放出速度が小さい場合があるため、大きな水素放出速度が要求される水素供給装置では、水素貯蔵量の多い水素貯蔵材料の使用が困難であった。一方で、水素エンジン自動車や燃料電池車等に搭載される水素貯蔵タンクを備えた水素供給装置では、多量の水素を貯蔵可能な形態とすることが好ましい。それゆえ、水素吸蔵量が多く、かつ、水素放出速度が大きい水素供給装置の開発が望まれている。 When hydrogen is stored using a hydrogen storage material, it is effective to store it in a hydrogen storage material having a large amount of hydrogen storage. However, because hydrogen storage materials with a large amount of hydrogen storage may have a low hydrogen release rate, it is difficult to use a hydrogen storage material with a large amount of hydrogen storage in a hydrogen supply device that requires a high hydrogen release rate. It was. On the other hand, it is preferable that the hydrogen supply device provided with a hydrogen storage tank mounted on a hydrogen engine vehicle, a fuel cell vehicle, or the like can store a large amount of hydrogen. Therefore, it is desired to develop a hydrogen supply device that has a large hydrogen storage amount and a high hydrogen release rate.
本発明は、かかる観点からなされたものであり、その要旨は、水素吸蔵量が多く、水素放出速度が小さい水素貯蔵材料が備えられていても、必要とされる水素放出量を長期間に亘って確保することが可能な水素供給装置、及び、当該水素供給装置を備える燃料電池システムを提供することにある。 The present invention has been made from such a viewpoint, and the gist thereof is that even if a hydrogen storage material having a large hydrogen storage amount and a low hydrogen release rate is provided, the required hydrogen release amount can be maintained over a long period of time. It is an object of the present invention to provide a hydrogen supply device that can be secured and a fuel cell system including the hydrogen supply device.
以下、図面を参照しつつ、本発明の水素供給装置及び燃料電池システムについて説明する。なお、以下の説明では、本発明の水素供給装置及び燃料電池システムが燃料電池車に搭載された場合を例示するが、以下に示す形態はあくまでも例示であり、本発明は以下の形態に限定されるものではない。 Hereinafter, the hydrogen supply device and the fuel cell system of the present invention will be described with reference to the drawings. In the following description, a case where the hydrogen supply device and the fuel cell system of the present invention are mounted on a fuel cell vehicle is illustrated, but the modes shown below are merely examples, and the present invention is limited to the following modes. It is not something.
１．水素供給装置
図１は、本発明にかかる水素供給装置の水素貯蔵手段に収容される、第１の水素貯蔵材料（以下「水素貯蔵材料Ａ」という。）のＰＣＴ曲線、及び、第２の水素貯蔵材料（以下「水素貯蔵材料Ｂ」という。）のＰＣＴ曲線の形態例を示す概念図であり、同一温度におけるＰＣＴ曲線の形態を示している。図２は、水素が充填されている途中の時点における、水素貯蔵手段の圧力と、水素貯蔵材料Ａの水素吸蔵圧及び水素放出圧並びに水素貯蔵材料Ｂの水素吸蔵圧及び水素放出圧（以下「水素貯蔵材料の水素吸放出特性」という。）との関係を示す概念図である。図３は、水素充填完了後に、水素貯蔵手段から水素が短時間で大量に放出される状態で燃料電池車が運転された場合における、水素貯蔵手段の圧力と、水素貯蔵材料の水素吸放出特性との関係を示す概念図である。図４は、図３に示す状態を経た後に、水素貯蔵手段から放出される水素が所定値以下の状態で燃料電池車が運転された場合における、水素貯蔵手段の圧力と、水素貯蔵材料の水素吸放出特性との関係を示す概念図である。図５は、図４に示す状態を経た後に、水素貯蔵手段から水素が短時間で大量に放出される状態で燃料電池車が運転された場合における、水素貯蔵手段の圧力と、水素貯蔵材料の水素吸放出特性との関係を示す概念図である。図１〜図５の縦軸は圧力［ＭＰａ］、同横軸は、水素貯蔵材料の固相中に貯蔵された水素原子Ｈと当該水素貯蔵材料を構成する金属原子Ｍとの質量比Ｈ／Ｍである。以下、図１〜図５を参照しつつ、本発明の水素供給装置について説明する。
1. FIG. 1 shows a PCT curve of a first hydrogen storage material (hereinafter referred to as “hydrogen storage material A”) and a second hydrogen stored in the hydrogen storage means of the hydrogen supply apparatus according to the present invention. It is a conceptual diagram which shows the form example of the PCT curve of a storage material (henceforth "hydrogen storage material B"), and has shown the form of the PCT curve in the same temperature. FIG. 2 shows the pressure of the hydrogen storage means, the hydrogen storage pressure and hydrogen release pressure of the hydrogen storage material A, and the hydrogen storage pressure and hydrogen release pressure of the hydrogen storage material B (hereinafter “ It is a conceptual diagram showing a relationship with “hydrogen absorption / release characteristics of a hydrogen storage material”. FIG. 3 shows the pressure of the hydrogen storage means and the hydrogen absorption / release characteristics of the hydrogen storage material when the fuel cell vehicle is operated in a state where a large amount of hydrogen is released from the hydrogen storage means in a short time after hydrogen filling is completed. It is a conceptual diagram which shows the relationship. FIG. 4 shows the pressure of the hydrogen storage means and the hydrogen of the hydrogen storage material when the fuel cell vehicle is operated after the state shown in FIG. 3 and the hydrogen released from the hydrogen storage means is below a predetermined value. It is a conceptual diagram which shows the relationship with an absorption / release characteristic. FIG. 5 shows the pressure of the hydrogen storage means when the fuel cell vehicle is operated in a state where a large amount of hydrogen is released from the hydrogen storage means in a short time after the state shown in FIG. It is a conceptual diagram which shows the relationship with a hydrogen absorption / release characteristic. 1 to 5, the vertical axis represents pressure [MPa], and the horizontal axis represents the mass ratio H / H of hydrogen atoms H stored in the solid phase of the hydrogen storage material and metal atoms M constituting the hydrogen storage material. M. Hereinafter, the hydrogen supply apparatus of the present invention will be described with reference to FIGS.
１．１．水素充填時
図１に示すように、本発明にかかる水素供給装置の水素貯蔵手段に収容される水素貯蔵材料Ａは、ＰＣＴ曲線のプラトー領域の圧力が、Ｐ１及びＰ２であり、水素貯蔵材料Ｂは、ＰＣＴ曲線のプラトー領域の圧力がＰ３及びＰ４である。すなわち、水素貯蔵材料Ａの水素吸蔵圧及び水素放出圧はＰ１及びＰ２、水素貯蔵材料Ｂの水素吸蔵圧及び水素放出圧はＰ３及びＰ４であって、Ｐ１、Ｐ２、Ｐ３、及び、Ｐ４の間には、Ｐ４＜Ｐ３＜Ｐ２＜Ｐ１の関係が成立する。
1.1. At the time of hydrogen filling As shown in FIG. 1, the hydrogen storage material A accommodated in the hydrogen storage means of the hydrogen supply apparatus according to the present invention has a pressure in the plateau region of the PCT curve of P1 and P2, and The pressure in the plateau region of the PCT curve is P3 and P4. That is, the hydrogen storage pressure and hydrogen release pressure of the hydrogen storage material A are P1 and P2, and the hydrogen storage pressure and hydrogen release pressure of the hydrogen storage material B are P3 and P4, respectively, between P1, P2, P3, and P4. The relationship P4 <P3 <P2 <P1 is established.
図１に示す水素吸放出特性を有する水素貯蔵材料Ａ及び水素貯蔵材料Ｂを収容した水素貯蔵手段に水素を充填させると、水素貯蔵手段の内部圧力ＰがＰ＜Ｐ３である間は、水素貯蔵材料Ａ及び水素貯蔵材料Ｂに吸蔵される水素は僅かな量に留まる。その後、水素貯蔵手段に充填された水素量が増大することにより、水素貯蔵手段の内部圧力ＰがＰ＝Ｐ３になると、水素吸蔵圧がＰ３である水素貯蔵材料Ｂに多量の水素が吸蔵される。一方、水素貯蔵材料Ａの水素吸蔵圧はＰ１（＞Ｐ３）であるため、水素貯蔵材料Ｂに多量の水素が吸蔵される状態であっても、水素貯蔵材料Ａに吸蔵される水素は依然として僅かな量に留まる。 When the hydrogen storage means containing the hydrogen storage material A and the hydrogen storage material B having the hydrogen absorption / release characteristics shown in FIG. 1 is filled with hydrogen, while the internal pressure P of the hydrogen storage means is P <P3, the hydrogen storage means Only a small amount of hydrogen is stored in the material A and the hydrogen storage material B. Thereafter, when the amount of hydrogen charged in the hydrogen storage means increases, when the internal pressure P of the hydrogen storage means reaches P = P3, a large amount of hydrogen is stored in the hydrogen storage material B whose hydrogen storage pressure is P3. . On the other hand, since the hydrogen storage pressure of the hydrogen storage material A is P1 (> P3), even when a large amount of hydrogen is stored in the hydrogen storage material B, only a small amount of hydrogen is stored in the hydrogen storage material A. Stay in the right amount.
水素貯蔵材料Ｂに多量の水素が吸蔵された後も水素貯蔵手段に水素を供給し続けると、やがて、水素貯蔵手段の内部圧力ＰがＰ＞Ｐ３となり、その後、Ｐ＝Ｐ１へと上昇する。水素貯蔵手段の内部圧力ＰがＰ＝Ｐ１になると、水素吸蔵圧がＰ１である水素貯蔵材料Ａに多量の水素が吸蔵される。そして、水素吸蔵材料Ａに多量の水素が吸蔵された後、水素貯蔵手段の内部圧力が所定値にまで到達すると、水素の充填が終了される。すなわち、水素貯蔵手段への水素の充填が完了した時点における、水素貯蔵手段の内部圧力Ｐは、Ｐ１＜Ｐとなる（図２参照）。なお、上記の水素吸放出特性を有する水素貯蔵材料Ａ及び水素貯蔵材料Ｂは、多くの場合、水素貯蔵材料Ｂよりも水素貯蔵材料Ａの方が水素吸蔵量が大きく、水素貯蔵材料Ｂよりも水素貯蔵材料Ａの方が水素の放出速度が小さい傾向が認められる。 If hydrogen is continuously supplied to the hydrogen storage means even after a large amount of hydrogen is occluded in the hydrogen storage material B, the internal pressure P of the hydrogen storage means eventually becomes P> P3, and then increases to P = P1. When the internal pressure P of the hydrogen storage means becomes P = P1, a large amount of hydrogen is stored in the hydrogen storage material A whose hydrogen storage pressure is P1. Then, after a large amount of hydrogen is stored in the hydrogen storage material A, when the internal pressure of the hydrogen storage means reaches a predetermined value, the filling of hydrogen is terminated. That is, the internal pressure P of the hydrogen storage unit at the time when the hydrogen storage unit is completely charged with hydrogen is P1 <P (see FIG. 2). In many cases, the hydrogen storage material A and the hydrogen storage material B having the above hydrogen storage / release characteristics have a larger hydrogen storage capacity than the hydrogen storage material B than the hydrogen storage material B. The hydrogen storage material A tends to have a lower hydrogen release rate.
１．２．走行時（その１）
水素充填の終了後に燃料電池車を始動させると、短時間に多量の水素が水素貯蔵手段から放出される。ところが、水素充填終了直後における水素貯蔵手段の内部圧力Ｐは、Ｐ１＜Ｐであり、かかる圧力状態において水素貯蔵材料Ａ及び水素貯蔵材料Ｂから放出される水素は、微量である。そのため、燃料電池車の始動直後には、水素貯蔵手段の内部に高圧ガスの状態で存在する水素（水素貯蔵材料Ａ及び水素貯蔵材料Ｂに吸蔵されず、水素貯蔵材料Ａ及び水素貯蔵材料Ｂの外側であって水素貯蔵手段の内部に存在する高圧ガスとしての水素）が、水素貯蔵手段から放出される。このようにして、高圧ガスの水素が水素貯蔵手段から放出されると、水素貯蔵手段の内部圧力Ｐは徐々に低下し、やがて、Ｐ＝Ｐ２となる。
1.2. When traveling (part 1)
When the fuel cell vehicle is started after the completion of hydrogen filling, a large amount of hydrogen is released from the hydrogen storage means in a short time. However, the internal pressure P of the hydrogen storage means immediately after the completion of hydrogen filling is P1 <P, and the hydrogen released from the hydrogen storage material A and the hydrogen storage material B in such a pressure state is very small. Therefore, immediately after the start of the fuel cell vehicle, hydrogen existing in the state of high-pressure gas in the hydrogen storage means (hydrogen storage material A and hydrogen storage material B are not occluded, but hydrogen storage material A and hydrogen storage material B Hydrogen as a high-pressure gas present outside and inside the hydrogen storage means) is released from the hydrogen storage means. In this way, when the hydrogen of the high pressure gas is released from the hydrogen storage means, the internal pressure P of the hydrogen storage means gradually decreases, and eventually P = P2.
Ｐ＝Ｐ２になると、本格的に、水素貯蔵材料Ａから水素が放出されるが、上述のように、水素貯蔵材料Ａは水素の放出速度が小さい。そのため、燃料電池車の加速時に必要とされる水素を、常に水素貯蔵材料Ａから放出される水素で賄うことができるとは限らない。その際には、水素貯蔵材料Ａから水素が本格的に放出され始めても、水素貯蔵手段の内部圧力Ｐは低下し続け、やがて、Ｐ＝Ｐ４になると考えられる。 When P = P2, hydrogen is released from the hydrogen storage material A in earnest, but as described above, the hydrogen storage material A has a low hydrogen release rate. Therefore, it is not always possible to cover the hydrogen required when accelerating the fuel cell vehicle with the hydrogen released from the hydrogen storage material A. At that time, even if hydrogen begins to be released from the hydrogen storage material A in earnest, the internal pressure P of the hydrogen storage means continues to decrease and eventually P = P4.
Ｐ＝Ｐ４になると、本格的に、水素貯蔵材料Ｂから水素が放出される。上述のように、水素貯蔵材料Ｂは水素の放出速度が大きい。そのため、Ｐ＝Ｐ４となって、水素貯蔵材料Ｂから多量の水素が放出されるようになると、必要とされる全ての量の水素を、水素貯蔵材料Ａから放出される水素及び水素貯蔵材料Ｂから放出される水素によって賄うことが可能になる。その結果、水素貯蔵手段の内部圧力Ｐは、Ｐ＝Ｐ４に維持され、以後、しばらくの間はＰ＝Ｐ４のまま、水素貯蔵手段から安定して水素が放出される（図３参照）。 When P = P4, hydrogen is released from the hydrogen storage material B in earnest. As described above, the hydrogen storage material B has a high hydrogen release rate. Therefore, when P = P4 and a large amount of hydrogen is released from the hydrogen storage material B, all the required amount of hydrogen is released from the hydrogen storage material A and the hydrogen storage material B. Can be covered by hydrogen released from the water. As a result, the internal pressure P of the hydrogen storage means is maintained at P = P4, and thereafter, hydrogen is stably released from the hydrogen storage means while maintaining P = P4 for a while (see FIG. 3).
１．３．走行時（その２）
図３に示す始動直後の状態に代表される、高負荷状態（燃料電池で所定量を超える水素が消費される状態。例えば、燃料電池車の急加速時等。）を経て、燃料電池車が低負荷状態（燃料電池で所定量以下の水素が消費される状態。燃料電池車の停止時も含む。）へ移行すると、水素貯蔵手段から取り出される水素量が減る。そうすると、水素貯蔵手段から取り出される水素の量よりも、水素貯蔵材料から放出される水素の方が多くなる。そのため、水素貯蔵手段の内部圧力Ｐは、Ｐ４＜Ｐとなり、やがて、Ｐ３≦Ｐ＜Ｐ２となる。水素貯蔵手段の内部圧力ＰがＰ３≦Ｐ＜Ｐ２の状態下では、水素放出圧がＰ２である水素貯蔵材料Ａから水素が放出される一方、水素吸蔵圧がＰ３である水素貯蔵材料Ｂへ水素が吸蔵される。それゆえ、かかる圧力状態下では、水素貯蔵材料Ａから放出された水素が水素貯蔵材料Ｂへと吸蔵され、見かけ上、水素が水素貯蔵材料Ａから水素貯蔵材料Ｂへと移動する（図４参照）。
1.3. When traveling (part 2)
The fuel cell vehicle is subjected to a high load state (a state where hydrogen exceeding a predetermined amount is consumed in the fuel cell, for example, when the fuel cell vehicle is suddenly accelerated) represented by a state immediately after the start shown in FIG. When shifting to a low load state (a state in which the fuel cell consumes a predetermined amount or less of hydrogen, including when the fuel cell vehicle is stopped), the amount of hydrogen taken out from the hydrogen storage means decreases. Then, the amount of hydrogen released from the hydrogen storage material is larger than the amount of hydrogen taken out from the hydrogen storage means. Therefore, the internal pressure P of the hydrogen storage means becomes P4 <P, and eventually P3 ≦ P <P2. Under the condition that the internal pressure P of the hydrogen storage means is P3 ≦ P <P2, hydrogen is released from the hydrogen storage material A whose hydrogen release pressure is P2, while hydrogen is supplied to the hydrogen storage material B whose hydrogen storage pressure is P3. Is occluded. Therefore, under such a pressure state, hydrogen released from the hydrogen storage material A is occluded into the hydrogen storage material B, and apparently hydrogen moves from the hydrogen storage material A to the hydrogen storage material B (see FIG. 4). ).
水素貯蔵材料Ａから水素貯蔵材料Ｂへの水素の移動は、水素貯蔵手段の内部圧力ＰがＰ３≦Ｐ＜Ｐ２である間に生じ、最終的に、水素貯蔵材料Ａに貯蔵されていた水素が全て放出された段階で、終了する。なお、水素貯蔵材料Ａから水素貯蔵材料Ｂへ水素が移動している間に、高負荷状態で燃料電池車が運転されると、水素貯蔵手段の内部圧力Ｐは、Ｐ＜Ｐ３となり、水素貯蔵材料Ａから水素貯蔵材料Ｂへの水素の移動は、一旦、終了する。しかし、燃料電池車が高負荷状態から低負荷状態へ移行すると、再び、水素貯蔵手段の内部圧力Ｐは、Ｐ３≦Ｐ＜Ｐ２となり、水素貯蔵材料Ａから水素貯蔵材料Ｂへ水素が移動する。結局、水素貯蔵手段の内部圧力ＰがＰ≦Ｐ１になった後は、水素貯蔵手段に新たに水素を充填しない限り、当該圧力ＰがＰ１＜Ｐとなることはない。そして、水素貯蔵材料Ａに貯蔵されていた水素は、水素貯蔵手段の外へと取り出されるか、又は、水素貯蔵材料Ｂに吸蔵されることによって底をつく。したがって、水素貯蔵手段に貯蔵されている水素の残量が少なくなると、水素貯蔵材料Ｂに水素が貯蔵され、水素貯蔵材料Ａには水素が貯蔵されていない状態となる。 The transfer of hydrogen from the hydrogen storage material A to the hydrogen storage material B occurs while the internal pressure P of the hydrogen storage means is P3 ≦ P <P2, and finally the hydrogen stored in the hydrogen storage material A is The process ends when all of the contents are released. When the fuel cell vehicle is operated in a high load state while hydrogen is moving from the hydrogen storage material A to the hydrogen storage material B, the internal pressure P of the hydrogen storage means becomes P <P3, and the hydrogen storage The transfer of hydrogen from the material A to the hydrogen storage material B is once terminated. However, when the fuel cell vehicle shifts from a high load state to a low load state, the internal pressure P of the hydrogen storage means again becomes P3 ≦ P <P2, and hydrogen moves from the hydrogen storage material A to the hydrogen storage material B. Eventually, after the internal pressure P of the hydrogen storage means becomes P ≦ P1, the pressure P does not become P1 <P unless the hydrogen storage means is newly filled with hydrogen. Then, the hydrogen stored in the hydrogen storage material A is taken out of the hydrogen storage means or stored in the hydrogen storage material B to bottom out. Therefore, when the remaining amount of hydrogen stored in the hydrogen storage means decreases, hydrogen is stored in the hydrogen storage material B, and no hydrogen is stored in the hydrogen storage material A.
１．４．走行時（その３）
図３及び図４に示す状態を経て、水素貯蔵手段に貯蔵されている水素の残量が少なくなり、水素貯蔵手段の内部圧力ＰがＰ＜Ｐ４になると、水素貯蔵材料Ａに貯蔵されていた水素は底をつき、原則として、水素貯蔵材料に貯蔵されている水素は、水素貯蔵材料Ｂに貯蔵されている水素のみになる（図５参照）。ここで、上述のように、水素貯蔵材料Ｂは、水素の放出速度が大きい。そのため、かかる状態になっても、水素貯蔵手段からは一度に多量の水素を取り出すことができる。
1.4. When traveling (part 3)
3 and 4, when the remaining amount of hydrogen stored in the hydrogen storage means decreases and the internal pressure P of the hydrogen storage means becomes P <P4, it is stored in the hydrogen storage material A. Hydrogen has a bottom, and in principle, the only hydrogen stored in the hydrogen storage material is hydrogen stored in the hydrogen storage material B (see FIG. 5). Here, as described above, the hydrogen storage material B has a high hydrogen release rate. Therefore, even in such a state, a large amount of hydrogen can be taken out from the hydrogen storage means at a time.
このように、本発明の水素供給装置によれば、最終的には、水素の放出速度が大きい水素貯蔵材料Ｂから水素が放出されるので、水素貯蔵手段に水素が貯蔵されている間は、燃料電池車に搭載された燃料電池で使用される単位時間当たりの水素量によらずに、必要とされる水素を確実に供給することができる。これに対し、従来のように、水素吸蔵量は多いが水素の放出速度が小さい水素吸蔵合金（例えば、上記水素貯蔵材料Ａ）のみが備えられる水素供給装置では、水素貯蔵タンク等に代表される水素貯蔵手段内の水素充填量が多い時には高圧ガスとして存在している水素を供給できるため、短時間は高負荷運転状態を維持できるものの、高圧ガスとして存在している水素が残り少なくなると、一度に多量の水素を取り出すことができず、結果として、高負荷運転を長時間に亘って維持することが困難であった。ところが、本発明の水素供給装置によれば、水素貯蔵材料Ａとともに、Ｐ４＜Ｐ３＜Ｐ２＜Ｐ１の関係を満たし水素の放出速度が大きい水素貯蔵材料Ｂが備えられる構成とすることで、当該水素貯蔵材料Ｂを水素貯蔵材料Ａのバッファタンクとして機能させ、水素の残量が少なくなっても大きな水素放出速度を維持することができる。それゆえ、本発明によれば、長期間に亘って高負荷運転状態を維持し得る、水素供給装置を提供することができる。 Thus, according to the hydrogen supply device of the present invention, since hydrogen is finally released from the hydrogen storage material B having a high hydrogen release rate, while hydrogen is stored in the hydrogen storage means, The required hydrogen can be reliably supplied irrespective of the amount of hydrogen per unit time used in the fuel cell mounted on the fuel cell vehicle. On the other hand, as in the conventional case, in a hydrogen supply apparatus provided with only a hydrogen storage alloy (for example, the hydrogen storage material A) having a large hydrogen storage amount but a low hydrogen release rate, it is represented by a hydrogen storage tank or the like. Since the hydrogen present as the high pressure gas can be supplied when the hydrogen filling amount in the hydrogen storage means is large, the high load operation state can be maintained for a short time, but when the remaining hydrogen as the high pressure gas decreases, A large amount of hydrogen could not be taken out. As a result, it was difficult to maintain a high load operation for a long time. However, according to the hydrogen supply device of the present invention, the hydrogen storage material A is provided with the hydrogen storage material B that satisfies the relationship of P4 <P3 <P2 <P1 and has a high hydrogen release rate. The storage material B functions as a buffer tank for the hydrogen storage material A, and a high hydrogen release rate can be maintained even when the remaining amount of hydrogen is reduced. Therefore, according to the present invention, it is possible to provide a hydrogen supply device that can maintain a high-load operation state for a long period of time.
本発明の水素供給装置において、水素貯蔵材料Ａ及び水素貯蔵材料Ｂの収容形態は、特に限定されるものではないが、水素貯蔵材料Ａ及び水素貯蔵材料Ｂとして水素吸蔵合金を用いる場合には、水素吸蔵時に発熱反応が生じ、水素放出時に吸熱反応が生じる。それゆえ、上記走行時（その２）に、水素貯蔵手段へ熱量を供給する熱量供給手段で消費されるエネルギーを低減し（又は、当該熱量供給手段を不要とし）て、エネルギーの利用効率を向上させ得る形態の水素供給装置を提供する等の観点からは、水素を吸蔵する水素貯蔵材料Ｂが発する熱を、水素を放出する水素貯蔵材料Ａが吸収可能な形態で、水素貯蔵材料Ａ及び水素貯蔵材料Ｂが収容されることが好ましい。かかる観点から、水素貯蔵材料Ａ及び水素貯蔵材料Ｂは、同一容器に収容されることが好ましい。 In the hydrogen supply device of the present invention, the storage form of the hydrogen storage material A and the hydrogen storage material B is not particularly limited, but when a hydrogen storage alloy is used as the hydrogen storage material A and the hydrogen storage material B, An exothermic reaction occurs when hydrogen is stored, and an endothermic reaction occurs when hydrogen is released. Therefore, during the travel (part 2), the energy consumed by the heat supply means that supplies heat to the hydrogen storage means is reduced (or the heat supply means is not required), and the energy use efficiency is improved. From the standpoint of providing a hydrogen supply device in a form that can be made to operate, the hydrogen storage material A that absorbs the heat generated by the hydrogen storage material B that stores hydrogen can be absorbed by the hydrogen storage material A that releases hydrogen. The storage material B is preferably accommodated. From this viewpoint, it is preferable that the hydrogen storage material A and the hydrogen storage material B are accommodated in the same container.
また、本発明にかかる水素供給装置の水素貯蔵手段に収容される、水素貯蔵材料Ａ及び水素貯蔵材料Ｂの質量は特に限定されるものではないが、水素貯蔵材料Ｂの質量が小さすぎると、水素貯蔵材料Ａに吸蔵された水素を水素貯蔵材料Ｂへ移動させ、水素貯蔵材料に貯蔵された水素の残量が少なくなった場合には、水素の放出速度が大きい水素貯蔵材料Ｂから水素を放出させる、という本発明の効果が得られ難い。一方、水素貯蔵材料Ａ及び水素貯蔵材料Ｂの合計量に占める水素貯蔵材料Ｂの割合が大きすぎると、水素貯蔵手段に貯蔵可能な水素量が低減する虞がある。そこで、本発明の水素供給装置では、これらの点を考慮して、水素貯蔵手段に収容される水素貯蔵材料Ａ及び水素貯蔵材料Ｂの質量を決定する事が好ましい。 Moreover, although the mass of the hydrogen storage material A and the hydrogen storage material B accommodated in the hydrogen storage means of the hydrogen supply apparatus according to the present invention is not particularly limited, if the mass of the hydrogen storage material B is too small, When the hydrogen stored in the hydrogen storage material A is moved to the hydrogen storage material B and the remaining amount of hydrogen stored in the hydrogen storage material decreases, hydrogen is released from the hydrogen storage material B having a high hydrogen release rate. It is difficult to obtain the effect of the present invention of releasing. On the other hand, if the ratio of the hydrogen storage material B to the total amount of the hydrogen storage material A and the hydrogen storage material B is too large, the amount of hydrogen that can be stored in the hydrogen storage means may be reduced. Therefore, in the hydrogen supply device of the present invention, it is preferable to determine the masses of the hydrogen storage material A and the hydrogen storage material B accommodated in the hydrogen storage means in consideration of these points.
本発明の水素供給装置で使用される水素貯蔵材料Ａ及び水素貯蔵材料Ｂは、Ｐ４＜Ｐ３＜Ｐ２＜Ｐ１の関係を満たし、かつ、水素貯蔵材料Ｂの水素放出速度が水素貯蔵材料Ａの水素放出速度よりも大きい材料であれば、特に限定されるものではなく、当該関係を満たす水素吸蔵合金等を好適に用いることができる。本発明の水素供給装置で使用可能な水素貯蔵材料Ａの具体例としては、ＴｉＣｒＶ等に代表されるＶを含有する体心立方構造を持つ合金や、Ｍｇ系合金のほか、ＡｌＨ４を含む錯体系材料等を挙げることができる。さらに、本発明の水素供給装置で使用可能な水素貯蔵材料Ｂの具体例としては、ＴｉＣｒＭｎ等に代表されるラーベス構造を持つ合金や、ＬａＮｉ５等に代表されるミッシュメタルを含む合金等を挙げることができる。 The hydrogen storage material A and the hydrogen storage material B used in the hydrogen supply apparatus of the present invention satisfy the relationship of P4 <P3 <P2 <P1, and the hydrogen release rate of the hydrogen storage material B is the hydrogen of the hydrogen storage material A. The material is not particularly limited as long as it is a material larger than the release rate, and a hydrogen storage alloy or the like that satisfies the relationship can be suitably used. Specific examples of the hydrogen storage material A that can be used in the hydrogen supply apparatus of the present invention include alloys having a body-centered cubic structure containing V typified by TiCrV and the like, Mg-based alloys, and complexes containing AlH 4. System materials can be mentioned. Further, specific examples of the hydrogen storage material B that can be used in the hydrogen supply apparatus of the present invention include alloys having a Laves structure typified by TiCrMn, alloys containing Misch metal typified by LaNi 5 and the like. be able to.
２．燃料電池システム
図６は、本発明の燃料電池システムの形態例を簡略化して示す概念図である。図６に示すように、本発明の燃料電池システム１０は、少なくとも上記水素貯蔵材料Ａ及び水素貯蔵材料Ｂを収容した水素貯蔵手段１、及び、当該水素貯蔵手段１から取り出された水素が流通する水素流通手段２、を備える水素供給装置３と、当該水素供給装置３から取り出された水素が供給される燃料電池４と、を備え、燃料電池４には、図示されていない酸化剤供給手段を介して酸化剤（例えば、空気等）が供給される。本発明の燃料電池システム１０が燃料電池車に搭載されると、燃料電池車の運転状態に応じて、燃料電池４で消費される水素量が変動し得る。ところが、上述のように、本発明の水素供給装置３の水素貯蔵手段１には、水素吸蔵量が多く水素放出速度が小さい水素貯蔵材料Ａに加えて、水素貯蔵材料Ｂが収容されている。そのため、燃料電池システム１０によれば、燃料電池車が低負荷状態で運転される場合のみならず、高負荷状態で運転される場合であっても、長期間に亘って、燃料電池４で必要とされる水素を供給することができる。したがって、本発明によれば、水素吸蔵量が多く、水素放出速度が小さい水素貯蔵材料Ａが備えられていても、必要とされる水素放出量を長期間に亘って確保することが可能な、燃料電池システム１０を提供することができる。
2. Fuel Cell System FIG. 6 is a conceptual diagram showing a simplified example of the fuel cell system according to the present invention. As shown in FIG. 6, in the fuel cell system 10 of the present invention, hydrogen storage means 1 containing at least the hydrogen storage material A and the hydrogen storage material B, and hydrogen taken out from the hydrogen storage means 1 circulate. A hydrogen supply device 3 having a hydrogen flow means 2 and a fuel cell 4 to which hydrogen extracted from the hydrogen supply device 3 is supplied. The fuel cell 4 has an oxidant supply means (not shown). An oxidizing agent (for example, air etc.) is supplied through it. When the fuel cell system 10 of the present invention is mounted on a fuel cell vehicle, the amount of hydrogen consumed by the fuel cell 4 may vary depending on the operating state of the fuel cell vehicle. However, as described above, the hydrogen storage means 1 of the hydrogen supply device 3 of the present invention contains the hydrogen storage material B in addition to the hydrogen storage material A having a large hydrogen storage amount and a low hydrogen release rate. Therefore, according to the fuel cell system 10, the fuel cell 4 is necessary not only when the fuel cell vehicle is operated in a low load state but also when the fuel cell vehicle is operated in a high load state. It is possible to supply hydrogen. Therefore, according to the present invention, even when the hydrogen storage material A having a large hydrogen storage amount and a low hydrogen release rate is provided, the required hydrogen release amount can be ensured over a long period of time. The fuel cell system 10 can be provided.
１…水素貯蔵手段
２…水素流通手段
３…水素供給装置
１０…燃料電池システム
DESCRIPTION OF SYMBOLS 1 ... Hydrogen storage means 2 ... Hydrogen distribution means 3 ... Hydrogen supply apparatus 10 ... Fuel cell system
Claims (2)
前記第２の水素貯蔵材料の水素吸蔵圧は、前記第１の水素貯蔵材料の水素放出圧よりも低く、かつ、前記第２の水素貯蔵材料の水素放出速度は、前記第１の水素貯蔵材料の水素放出速度よりも大きく、
前記第１の水素貯蔵材料及び前記第２の水素貯蔵材料が同一容器に収容されていることを特徴とする、水素供給装置。 Comprising hydrogen storage means containing at least a first hydrogen storage material and a second hydrogen storage material;
The hydrogen storage pressure of the second hydrogen storage material is lower than the hydrogen release pressure of the first hydrogen storage material, and the hydrogen release rate of the second hydrogen storage material is the first hydrogen storage material. much larger than the hydrogen evolution rate,
The hydrogen supply apparatus, wherein the first hydrogen storage material and the second hydrogen storage material are accommodated in the same container .
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