JP2000351603A - Hydrogen absorbing and desorbing fluid - Google Patents
Hydrogen absorbing and desorbing fluidInfo
- Publication number
- JP2000351603A JP2000351603A JP11162599A JP16259999A JP2000351603A JP 2000351603 A JP2000351603 A JP 2000351603A JP 11162599 A JP11162599 A JP 11162599A JP 16259999 A JP16259999 A JP 16259999A JP 2000351603 A JP2000351603 A JP 2000351603A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- fine particles
- hydrogen storage
- release
- fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- Y02E60/32—Hydrogen storage
Landscapes
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は水素吸蔵放出流体に
関する。[0001] The present invention relates to a hydrogen storage / release fluid.
【０００２】[0002]
【従来の技術】水素吸蔵合金などの水素吸蔵能および水
素放出能が良好な物質が提供されている。この物質とし
てはパラジウム系、希土類元素系等が代表的なものであ
る。このものでは、吸蔵させた水素を適宜放出させ、水
素を利用することができる。この物質はバルク体または
粉粒状として使用されている。2. Description of the Related Art Materials having good hydrogen storage ability and hydrogen release ability, such as a hydrogen storage alloy, have been provided. Representative examples of this substance include a palladium-based substance and a rare-earth element-based substance. In this case, the occluded hydrogen is appropriately released, and the hydrogen can be used. This material is used as a bulk or a powder.
【０００３】[0003]
【発明が解決しようとする課題】上記した水素吸蔵能お
よび水素放出能を備えた物質は、バルク体または粉粒状
であり、配管による移送等が困難となり、使用形態は制
約される。そこで近年、本発明者らは、水素吸蔵能およ
び水素放出能を有する微粒子を溶媒中に分散させた水素
吸蔵放出流体を開発している。The above-mentioned substances having the hydrogen storage ability and the hydrogen release ability are in the form of a bulk or a powder, and are difficult to be transported by piping, so that the use form is restricted. Therefore, in recent years, the present inventors have developed a hydrogen storage / release fluid in which fine particles having hydrogen storage / release properties are dispersed in a solvent.
【０００４】しかしこの水素吸蔵放出流体では、放置時
間が長くなると、水素吸蔵能および水素放出能を有する
微粒子が沈降してしまう。この場合、水素吸蔵放出流体
の濃度は不均一となる。微粒子の粒径を小さくすれば、
微粒子の沈降はある程度は抑えられるものの、水素吸蔵
放出流体の放置期間が長期化すれば、凝集により微粒子
の粒径が増加し、やはり沈降してしまう。[0004] However, in this hydrogen storage and release fluid, if the standing time is long, fine particles having a hydrogen storage capacity and a hydrogen release capacity settle. In this case, the concentration of the hydrogen storage / release fluid becomes non-uniform. By reducing the particle size of the fine particles,
Although the sedimentation of the fine particles can be suppressed to some extent, if the storage period of the hydrogen storage / release fluid is prolonged, the particle diameter of the fine particles increases due to agglomeration, which also causes sedimentation.
【０００５】また微粒子の粒径を小さくした場合には、
微粒子が酸化等の被毒により劣化し易くなり、水素吸蔵
および水素放出を繰り返すサイクル数が増加すると、水
素吸蔵放出流体は劣化し、目標とする水素吸蔵能を得に
くくなる。本発明は上記した実情に鑑みてなされたもの
であり、放置時間が長くなっても微粒子の沈降を抑制で
き、更に水素吸蔵および水素放出を繰り返すサイクル数
が増加しても劣化を抑制するのに有利な水素吸蔵放出流
体を提供することを課題とする。When the particle size of the fine particles is reduced,
When the number of cycles in which hydrogen storage and release are repeated increases, the hydrogen storage and release fluid deteriorates and it becomes difficult to obtain a target hydrogen storage capacity. The present invention has been made in view of the above-described circumstances, and it is possible to suppress the sedimentation of fine particles even when the standing time is long, and to further suppress deterioration even when the number of cycles of repeating hydrogen storage and hydrogen release is increased. It is an object to provide an advantageous hydrogen storage and release fluid.
【０００６】[0006]
【課題を解決するための手段】本発明の水素吸蔵放出流
体は、水素吸蔵能および水素放出能を有する微粒子を溶
媒中に分散させると共に、微粒子の沈降を抑える沈降抑
制物質が含まれていることを特徴とするものである。The hydrogen storage and release fluid of the present invention contains fine particles having a hydrogen storage ability and a hydrogen release ability dispersed in a solvent and contains a sedimentation suppressing substance which suppresses the sedimentation of the fine particles. It is characterized by the following.
【０００７】[0007]
【発明の実施の形態】本発明においては、水素吸蔵能お
よび水素放出能を有する微粒子としては、水素吸蔵能お
よび水素放出能に富む微粒子を採用することができる。
例えば、公知の水素吸蔵物質（例えば水素吸蔵能および
水素放出能に富む遷移元素、希土類元素の少なくとも１
種）を採用することができる。具体的には水素吸蔵物質
としては、パラジウム、パラジウム系合金、希土類元素
系（Ｌａ系、Ｃｅ系等：ミッシュメタル、Ｌａリッチの
ミッシュメタルを含む）、Ｆｅ−Ｔｉ系合金、Ｍｇ、Ｍ
ｇ系合金、Ｚｒ、Ｚｒ系合金等の水素吸蔵合金の少なく
とも１種を採用することができる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as the fine particles having a hydrogen absorbing ability and a hydrogen releasing ability, fine particles having a high hydrogen absorbing ability and a hydrogen releasing ability can be employed.
For example, a known hydrogen storage material (for example, at least one of a transition element and a rare earth element that are rich in hydrogen storage capacity and hydrogen release capacity)
Species) can be employed. Specifically, as the hydrogen storage material, palladium, palladium-based alloy, rare earth element-based (La-based, Ce-based, etc .: misch metal, La-rich misch metal), Fe-Ti-based alloy, Mg, M
At least one kind of hydrogen storage alloy such as a g-based alloy, Zr, or a Zr-based alloy can be employed.
【０００８】微粒子の平均粒径は、微粒子の水素吸蔵能
および水素放出能、微粒子の製造形態、溶媒の種類、沈
降抑制物質の種類、水素吸蔵放出流体に要請される沈降
抑制能、水素吸蔵放出流体の製造コストなどの要因を考
慮して適宜選択することができる。微粒子成分を含む溶
液から還元反応を利用して微粒子を生成する場合には、
微粒子はオングストローム、ナノメータ（ｎｍ）単位に
基づいた超微細形態を形成し易い。水素吸蔵能を備えた
バルク体や粉粒体から物理的粉砕で粉砕して微粒子を生
成する場合には、微粒子はナノメータ（ｎｍ）単位、マ
イクロメータ（μｍ）単位に基づいた微細形態を形成し
易い。The average particle size of the fine particles is determined by the hydrogen storage capacity and hydrogen release capacity of the fine particles, the production form of the fine particles, the type of the solvent, the type of the sedimentation suppressing substance, the sedimentation suppressing ability required for the hydrogen storage and release fluid, and the hydrogen storage and release. It can be appropriately selected in consideration of factors such as the production cost of the fluid. When using a reduction reaction from a solution containing fine particle components to generate fine particles,
Fine particles are liable to form an ultrafine morphology based on angstrom and nanometer (nm) units. When fine particles are produced by physical pulverization from a bulk material or a granular material having a hydrogen storage ability, the fine particles form a fine morphology based on a nanometer (nm) unit or a micrometer (μm) unit. easy.
【０００９】従って、微粒子の平均粒径の下限値として
は、例えば、５オングストローム、１０オングストロー
ム、２０オングストローム、３０オングストローム、５
０オングストローム（=５ｎｍ）、１０ｎｍ、２０ｎｍ
等を選択することができるが、これに限定されるもので
はない。微粒子の平均粒径の上限値としては、例えば、
２０μｍ、１０μｍ、１μｍ、５００ｎｍ、１００ｎ
ｍ、５０ｎｍ、１０ｎｍ、５ｎｍ等を選択することがで
きるが、これに限定されるものではない。Therefore, the lower limit of the average particle diameter of the fine particles is, for example, 5 Å, 10 Å, 20 Å, 30 Å, 5 Å or 5 Å.
0 Å (= 5 nm), 10 nm, 20 nm
Can be selected, but the present invention is not limited to this. As the upper limit of the average particle diameter of the fine particles, for example,
20 μm, 10 μm, 1 μm, 500 nm, 100 n
m, 50 nm, 10 nm, 5 nm or the like can be selected, but is not limited thereto.
【００１０】従って本発明によれば、水素吸蔵能および
水素放出能を有する微粒子としては、１ｎｍ〜１μｍの
平均粒子径をもつ粒子（コロイド粒子）を採用すること
ができる。溶媒としては、水素吸蔵能および水素放出能
を有する微粒子を分散させ得るものであればよく、水系
溶媒、有機溶媒などを用いることができる。例えば、
水、アルコール（メタノール、エタノール、プロパノー
ル、ブタノール、アミルアルコール、エチレングリコー
ルなど）、オイル（シリコーンオイル、ケロシン等）
等、あるいは、これらの混合物の少なくとも１種を採用
することができる。溶媒としては、微粒子や沈降抑制物
質の種類に応じて、極性が大きな溶媒（極性が大きいＯ
Ｈ基をもつ水、メタノール、エタノールなど）、極性が
小さいか無極性の溶媒を適宜採用することができる。Therefore, according to the present invention, particles (colloidal particles) having an average particle diameter of 1 nm to 1 μm can be employed as the fine particles having a hydrogen absorbing ability and a hydrogen releasing ability. Any solvent can be used as long as it can disperse fine particles having a hydrogen absorbing ability and a hydrogen releasing ability, and an aqueous solvent, an organic solvent and the like can be used. For example,
Water, alcohol (methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol, etc.), oil (silicone oil, kerosene, etc.)
Or at least one of these mixtures. As the solvent, a solvent having a large polarity (O 2 having a large polarity)
Water having an H group, methanol, ethanol, or the like) and a solvent having a small polarity or a non-polarity can be appropriately used.
【００１１】例えば、微粒子または沈降抑制物質が極性
を有するときには、極性が大きな溶媒を用いることがで
きる。あるいは、微粒子または沈降抑制物質が無極性ま
たは極性が小さいときには、無極性かまたは極性が小さ
い溶媒を適宜採用することができる。沈降抑制物質は微
粒子の沈降を抑えるものである。沈降抑制物質は、微粒
子を分散する溶媒に対して親和性をもつものが好まし
い。沈降抑制物質は、微粒子の表面に被覆されて複合化
されている形態を採用することができる。このような沈
降抑制物質としては、微粒子を分散させる溶媒に可溶で
あることが好ましく、水系溶媒であれば水に可溶な物
質、有機溶媒であれば有機溶媒に可溶な物質を採用する
ことができる。For example, when the fine particles or the sedimentation inhibiting substance have a polarity, a solvent having a large polarity can be used. Alternatively, when the fine particles or the sedimentation inhibiting substance are non-polar or low in polarity, a non-polar or low-polarity solvent can be appropriately employed. The sedimentation suppressing substance suppresses sedimentation of fine particles. The sedimentation inhibitor preferably has an affinity for the solvent in which the fine particles are dispersed. The sedimentation-suppressing substance can adopt a form in which the surface of the fine particles is coated and complexed. As such a sedimentation suppressing substance, it is preferable that the substance is soluble in a solvent in which the fine particles are dispersed. In the case of an aqueous solvent, a substance soluble in water, and in the case of an organic solvent, a substance soluble in an organic solvent is used. be able to.
【００１２】沈降抑制物質を微粒子の表面に被覆して複
合化する形態としては、モノマーを表面に付着させ、こ
れを重合させてポリマーとする形態、あるいは、微粒子
とポリマーとを物理的に混合することにより複合化する
形態などを採用することができる。ポリマーとしては、
ポリビニルピロリドン、ポリビニルアルコール、ポリア
クリル酸、ポリアクリルアミド、ポリアクリロニトリ
ル、ポリスルホン酸、ポリエーテル等の少なくも１種を
採用することができる。[0012] The form in which the precipitation-inhibiting substance is coated on the surface of the fine particles to form a composite is as follows: a monomer is attached to the surface and polymerized to form a polymer, or the fine particles and the polymer are physically mixed. Accordingly, a composite form can be adopted. As a polymer,
At least one of polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyacrylonitrile, polysulfonic acid, polyether and the like can be used.
【００１３】また、沈降抑制物質として機能できる界面
活性剤を用い、界面活性剤を微粒子の表面に付着する形
態などを採用することができる。水系溶媒の場合、微粒
子の表面が疎水性をもつときには、界面活性剤の疎水基
が微粒子側に向き、界面活性剤の親水基が溶媒に向くた
め、微粒子の親水性が強くなり、微粒子が分散し易くな
る。[0013] In addition, it is possible to adopt a form in which a surfactant which can function as a settling inhibitor is used, and the surfactant is attached to the surface of the fine particles. In the case of an aqueous solvent, when the surface of the fine particles has hydrophobicity, the hydrophobic groups of the surfactant face the fine particles, and the hydrophilic groups of the surfactant face the solvent. Easier to do.
【００１４】図４は微粒子の代表的な形態を模式化して
示す。図４に示すように、水素吸蔵能および水素放出能
を有する微粒子１００の周りに、沈降抑制物質としての
ポリマー２００が被覆されている。この場合、沈降抑制
物質としてのポリマー２００と、ポリマー２００の周囲
の溶媒との相互作用（静電気的相互作用、配位結合な
ど）により、微粒子を溶媒に分散させることができる。FIG. 4 schematically shows a typical form of the fine particles. As shown in FIG. 4, a polymer 200 as a sedimentation suppressing substance is coated around fine particles 100 having a hydrogen storage ability and a hydrogen release ability. In this case, the fine particles can be dispersed in the solvent by the interaction between the polymer 200 as the precipitation-preventing substance and the solvent around the polymer 200 (electrostatic interaction, coordination bond, etc.).
【００１５】水素吸蔵放出流体においては水素吸蔵能は
確保される。殊に、水素を吸蔵させる際に、水素吸蔵放
出流体に水素ガスを吹き込んで水素吸蔵放出流体をバブ
リング処理すれば、ポリマーと微粒子との良好なる相対
変位が期待できるため、水素吸蔵能は確保される。水素
吸蔵放出流体から水素を放出する際には、水素吸蔵放出
流体を所定の加熱温度領域に適宜加熱すれば、微粒子か
らの水素放出能は確保される。微粒子の材質、溶媒の材
質、単位時間当たりに要請されている水素放出量などの
要因に応じて、加熱温度領域は適宜選択できるものの、
例えば、４０〜６０℃程度、あるいは８０〜１２０℃程
度にできる。但しこれに限定されるものではない。In the hydrogen storage / release fluid, the hydrogen storage capacity is secured. In particular, when hydrogen is absorbed and hydrogen gas is blown into the hydrogen storage and release fluid to perform a bubbling process on the hydrogen storage and release fluid, good relative displacement between the polymer and the fine particles can be expected, so that the hydrogen storage capacity is secured. You. When releasing hydrogen from the hydrogen storage and release fluid, the hydrogen storage capability can be ensured by appropriately heating the hydrogen storage and release fluid to a predetermined heating temperature range. Depending on factors such as the material of the fine particles, the material of the solvent, and the amount of hydrogen release required per unit time, the heating temperature range can be appropriately selected,
For example, it can be set to about 40 to 60 ° C or about 80 to 120 ° C. However, it is not limited to this.
【００１６】[0016]
【実施例】（実施例１）以下、本発明の実施例１を説明
する。塩化パラジウム（ＰｄＣｌ2）を塩酸水溶液に溶
解させ、６ｍＭ（Ｍ：モル濃度）の塩素化水素パラジウ
ム（Ｈ2ＰｄＣｌ4）の水溶液を調整した。また塩化銀
（ＡｇＣｌ）を塩酸水溶液に溶解させ、６ｍＭ（Ｍ=モ
ル濃度=ｍｏｌ／Ｌ）の塩素化水素銀（ＨＡｇＣｌ2）の
水溶液を調整した。(Embodiment 1) Hereinafter, Embodiment 1 of the present invention will be described. Palladium chloride (PdCl 2 ) was dissolved in an aqueous hydrochloric acid solution to prepare a 6 mM (M: molar concentration) aqueous solution of palladium hydrogen chloride (H 2 PdCl 4 ). In addition, silver chloride (AgCl) was dissolved in an aqueous hydrochloric acid solution to prepare an aqueous solution of 6 mM (M = molar concentration = mol / L) of silver hydrogen chloride (HAgCl 2 ).
【００１７】塩素化水素パラジウム（Ｈ2ＰｄＣｌ4）の
水溶液（Ｐｄ換算で４８０μｍｏｌ）と、塩素化水素銀
（ＨＡｇＣｌ2）の水溶液（Ａｇ換算で１２０μｍｏ
ｌ）との両者を混合した。更に、後工程で留去される第
１溶媒として水４００ｍｌおよびエタノール１６０ｍｌ
とを加え、更に、安定化ポリマーとしてポリビニルピロ
リドン（Ｎ−ビニル−２ピロリドンのポリマー：以下、
ＰＶＰとも記す）を６ｍｍｏｌを加え、混合溶液を形成
した。そしてその混合溶液をオイルバスで１００℃で２
時間、加熱環流した。An aqueous solution of palladium hydrogen chloride (H 2 PdCl 4 ) (480 μmol in terms of Pd) and an aqueous solution of silver hydrogen chloride (HAgCl 2 ) (120 μmol in terms of Ag)
l) were mixed. Furthermore, 400 ml of water and 160 ml of ethanol are used as the first solvent distilled off in the subsequent step.
Further, as a stabilizing polymer, polyvinylpyrrolidone (a polymer of N-vinyl-2-pyrrolidone: hereinafter,
6 mmol was added to form a mixed solution. Then, the mixed solution is placed in an oil bath at 100 ° C. for 2 hours.
Reflux with heating for hours.
【００１８】放冷後に、ホウ素化水素カリウムを２０ｍ
ｏｌ加え、２４時間攪拌した後に、溶媒を留去し、固形
物を形成した。この固形物は、Ｐｄ−Ａｇ系の微粒子
に、沈降抑制物質として機能できるＰＶＰのポリマーが
被覆されて構成されている。この微粒子の合金組成はＰ
ｄ−Ａｇ合金であり、ａｔ％でＰｄ：Ａｇ=８０：２０
であった。After allowing to cool, potassium borohydride is added to 20 m
After stirring for 24 hours, the solvent was distilled off to form a solid. This solid is composed of Pd-Ag-based fine particles coated with a PVP polymer that can function as a settling inhibitor. The alloy composition of these fine particles is P
It is a d-Ag alloy, and Pd: Ag = 80: 20 at%.
Met.
【００１９】その固形物を所定の溶媒（２−ブトキシエ
タノール：極性溶媒）に分散させ、表１に示す４種類の
水素吸蔵放出流体（試料Ａ〜試料Ｅ）を形成した。この
場合、金属量は５ｇであり、水素吸蔵放出流体に占める
濃度として１０ｗｔ％である。この流体５０ｃｍ3を以
下のＰＣＴ特性測定に供した。４種類の水素吸蔵放出流
体（試料Ａ〜試料Ｅ）について、ＰＣＴ特性を試験し、
水素の最大吸蔵量を求めた。この場合、水素吸蔵操作は
０℃で行い目標水素平衡圧を１ＭＰａとし、水素放出操
作は１００℃で行い目標水素平衡圧を０．１ＭＰａとし
た。水素吸蔵操作および水素放出操作を１回づつ行うこ
とを１サイクルとし、このサイクルを繰り返し、最大吸
蔵量の変化を試験した。The solid was dispersed in a predetermined solvent (2-butoxyethanol: polar solvent) to form four types of hydrogen storage / release fluids shown in Table 1 (Samples A to E). In this case, the amount of metal is 5 g, and the concentration in the hydrogen storage-release fluid is 10 wt%. 50 cm 3 of this fluid was subjected to the following PCT characteristic measurement. PCT characteristics were tested for four types of hydrogen storage / release fluids (Samples A to E).
The maximum storage amount of hydrogen was determined. In this case, the hydrogen storage operation was performed at 0 ° C. to set the target hydrogen equilibrium pressure to 1 MPa, and the hydrogen release operation was performed at 100 ° C. to set the target hydrogen equilibrium pressure to 0.1 MPa. The cycle of performing the hydrogen storage operation and the hydrogen release operation once each was defined as one cycle, and this cycle was repeated to test the change in the maximum storage amount.
【００２０】更に比較例１として、上記実施例１の試料
Ａ〜試料Ｅの微粒子と同様の組成をもつ微粒子粉末（粒
子径は１０００ｎｍ，合金組成はａｔ％でＰｄ：Ａｇ=
８０：２０）を用い、その粉末を同様の溶媒に同一濃度
で分散させ、比較例１の水素吸蔵放出流体を形成した。
比較例１の水素吸蔵放出流体についても同様に試験し
た。Further, as Comparative Example 1, a fine particle powder having the same composition as the fine particles of Samples A to E of Example 1 (particle diameter is 1000 nm, alloy composition is at%, and Pd: Ag =
80:20), and the powder was dispersed in a similar solvent at the same concentration to form a hydrogen storage / release fluid of Comparative Example 1.
The hydrogen storage / release fluid of Comparative Example 1 was similarly tested.
【００２１】図１は試験結果を示す。図１の横軸はサイ
クル数を示す、縦軸は水素の最大吸蔵量［Ｈ／Ｍ］を示
す。［Ｈ／Ｍ］は１金属原子に対して吸蔵された水素原
子の個数を意味する。図１において、◆印は試料Ａの結
果を示し、■印は試料Ｂを示し、×印は試料Ｃの結果を
示し、□印は試料Ｄを示し、＊印は比較例１を示す。FIG. 1 shows the test results. The horizontal axis in FIG. 1 indicates the number of cycles, and the vertical axis indicates the maximum hydrogen storage amount [H / M]. [H / M] means the number of hydrogen atoms absorbed per metal atom. In FIG. 1, the mark “◆” indicates the result of Sample A, the mark “■” indicates the result of Sample B, the mark “X” indicates the result of Sample C, the mark □ indicates Sample D, and the mark “*” indicates Comparative Example 1.
【００２２】図１から理解できるように、比較例１で
は、サイクル数が増加するにつれて最大吸蔵量は大幅に
低下した。これに対して本実施例品に係る試料Ａ、試料
Ｂ、試料Ｃおよび試料Ｄでは、サイクル数が増加して
も、水素の最大吸蔵量はあまり低下しなかった。即ち、
サイクル数が１００サイクル、２００サイクル、３００
サイクル、４００サイクル、５００サイクルを越えて
も、水素の最大吸蔵量はあまり低下しなかった。As can be understood from FIG. 1, in Comparative Example 1, the maximum occlusion amount was greatly reduced as the number of cycles was increased. On the other hand, in the samples A, B, C, and D according to the products of the present example, even when the number of cycles was increased, the maximum hydrogen storage amount was not significantly reduced. That is,
100 cycles, 200 cycles, 300 cycles
Even when the number of cycles exceeded 400, 400, and 500, the maximum hydrogen storage amount did not decrease so much.
【００２３】更にサイクル劣化度および流体安定性を調
べた。サイクル劣化度とは、［（５００サイクル目の水
素吸蔵放出流体の最大吸蔵量）／（１サイクル目の水素
吸蔵放出流体の最大吸蔵量）］×１００％を意味する。
従ってサイクル劣化度の数値が小さいことは、劣化し易
いことを意味し、サイクル劣化度の数値が大きいこと
は、劣化しにくいことを意味する。流体安定性は、放置
を継続したとき水素吸蔵放出流体における微粒子の沈降
度合を目視で判定した。Further, the degree of cycle deterioration and fluid stability were examined. The cycle deterioration degree means [(maximum storage amount of hydrogen storage and release fluid in the 500th cycle) / (maximum storage amount of hydrogen storage and release fluid in the first cycle)] × 100%.
Therefore, a small numerical value of the cycle deterioration degree means that it is easy to deteriorate, and a large numerical value of the cycle deterioration degree means that it is hard to deteriorate. The fluid stability was determined by visually observing the degree of sedimentation of the fine particles in the hydrogen storage / release fluid when standing was continued.
【００２４】表１は試料Ａ〜試料Ｄおよび比較例１に係
る水素吸蔵放出流体の条件、サイクル劣化度および流体
安定性についての試験結果を示す。Table 1 shows the test results for the conditions, cycle deterioration degree and fluid stability of the hydrogen storage / release fluid according to Samples A to D and Comparative Example 1.
【００２５】[0025]
【表１】 表１に示すように、試料Ａでは、固形物のうちＰＶＰ重
量は９２ｗｔ％であり、微粒子の平均粒子径は２ｎｍで
あり、サイクル劣化度は８８％であり、２週間以上放置
しても水素吸蔵放出流体は安定であり、微粒子の沈降は
認められなかった。[Table 1] As shown in Table 1, in sample A, the PVP weight of the solid was 92 wt%, the average particle diameter of the fine particles was 2 nm, the degree of cycle deterioration was 88%, and hydrogen was observed even when left for two weeks or more. The occluding and releasing fluid was stable, and no sedimentation of fine particles was observed.
【００２６】試料Ｂでは、固形物のうちＰＶＰ重量は８
４ｗｔ％であり、微粒子の平均粒子径は５ｎｍであり、
サイクル劣化度は８６％であり、２週間以上放置しても
水素吸蔵放出流体は安定であった。試料Ｃでは、固形物
のうちＰＶＰ重量は７５ｗｔ％であり、微粒子の平均粒
子径は２ｎｍであり、サイクル劣化度は８４．５％であ
り、２週間以上放置しても水素吸蔵放出流体は安定であ
った。In sample B, the PVP weight of the solid material was 8
4 wt%, the average particle diameter of the fine particles is 5 nm,
The cycle deterioration degree was 86%, and the hydrogen storage / release fluid was stable even when left for two weeks or longer. In sample C, the PVP weight of the solid was 75 wt%, the average particle size of the fine particles was 2 nm, the degree of cycle deterioration was 84.5%, and the hydrogen storage / release fluid was stable even after standing for 2 weeks or more. Met.
【００２７】試料Ｄでは、固形物のうちＰＶＰ重量は６
３ｗｔ％であり、微粒子の平均粒子径は５ｎｍであり、
サイクル劣化度は８２．５％であり、２週間以上放置し
ても水素吸蔵放出流体は安定であった。比較例１では、
ＰＶＰ重量は０％であり、微粒子の平均粒子径は１００
０ｎｍであり、サイクル劣化度は３５％でありサイクル
劣化性が大きく、更に流体安定性の評価は『×』であ
り、かなりの沈降が確認された。In sample D, the PVP weight of the solid was 6
3 wt%, the average particle diameter of the fine particles is 5 nm,
The cycle deterioration degree was 82.5%, and the hydrogen storage / release fluid was stable even when left for two weeks or longer. In Comparative Example 1,
The PVP weight was 0%, and the average particle diameter of the fine particles was 100%.
It was 0 nm, the degree of cycle deterioration was 35%, the cycle deterioration was large, and the evaluation of fluid stability was "x", and considerable sedimentation was confirmed.
【００２８】上記した試験結果から、本実施例に係る試
料Ａ〜試料Ｄについては、水素吸蔵操作および水素放出
操作のサイクル数を多数回繰り返しても、水素吸蔵放出
流体の劣化を抑制でき、水素吸蔵能の低下を抑制できる
ことがわかる。更に長期間放置しても、微粒子の沈降を
抑制できることがわかる。長期間放置しても微粒子の沈
降を抑制できるのは、沈降抑制物質としてのＰＶＰが有
する官能基と、溶媒としてのエタノールが有するＯＨ基
との親和力によるものと推察される。From the above test results, regarding the samples A to D according to the present embodiment, even if the number of cycles of the hydrogen storage operation and the hydrogen release operation is repeated many times, the deterioration of the hydrogen storage and release fluid can be suppressed, It can be seen that a decrease in occlusion ability can be suppressed. It can be seen that the sedimentation of the fine particles can be suppressed even after being left for a long time. It is presumed that the sedimentation of the fine particles can be suppressed even after being left for a long period of time due to the affinity between the functional group of PVP as the sedimentation suppressing substance and the OH group of ethanol as the solvent.
【００２９】（実施例２）次に本発明の実施例２につい
て説明する。塩化パラジウム（ＰｄＣｌ2）を塩酸水溶
液に溶解させ、６ｍＭ（Ｍ：モル濃度）の塩素化水素パ
ラジウム（Ｈ2ＰｄＣｌ4）の水溶液を調整した。また塩
化白金（ＰｔＣｌ2）を塩酸水溶液に溶解させ、６ｍＭ
（Ｍ：モル濃度）の塩素化水素白金（Ｈ2ＰｔＣｌ6）の
水溶液を調整した。(Embodiment 2) Next, Embodiment 2 of the present invention will be described. Palladium chloride (PdCl 2 ) was dissolved in an aqueous hydrochloric acid solution to prepare a 6 mM (M: molar concentration) aqueous solution of palladium hydrogen chloride (H 2 PdCl 4 ). Platinum chloride (PtCl 2 ) is dissolved in an aqueous hydrochloric acid solution and 6 mM
(M: molar concentration) aqueous solution of platinum hydrochloride (H 2 PtCl 6 ) was prepared.
【００３０】塩素化水素パラジウム（Ｈ2ＰｄＣｌ4）の
水溶液（Ｐｄ換算で４８０μｍｏｌ）と、塩素化水素白
金（Ｈ2ＰｔＣｌ6）の水溶液（Ｐｔ換算で１２０μｍｏ
ｌ）との両者を混合した。更に、後工程で留去される第
１溶媒として水４００ｍｌおよびエタノール３００ｍｌ
を加え、更に安定化高分子としてポリビニルアルコール
（ＰＶＡとも記する）を６ｍｍｏｌを加え、混合溶液を
形成した。この混合溶液をオイルバスで１００℃で２時
間、加熱環流した。ポリビニルアルコール（ＰＶＡ）に
代えてポリアクリル酸（ＰＡＡとも記する）を６ｍｍｏ
ｌ加えたものについても、同様に形成した。An aqueous solution of palladium hydrogen chloride (H 2 PdCl 4 ) (480 μmol in terms of Pd) and an aqueous solution of platinum hydrogen chloride (H 2 PtCl 6 ) (120 μmol in terms of Pt)
l) were mixed. Further, 400 ml of water and 300 ml of ethanol were used as the first solvent distilled off in the subsequent step.
And 6 mmol of polyvinyl alcohol (also referred to as PVA) as a stabilizing polymer was added to form a mixed solution. This mixed solution was heated and refluxed at 100 ° C. for 2 hours in an oil bath. 6 mmo of polyacrylic acid (also referred to as PAA) instead of polyvinyl alcohol (PVA)
The same addition was made in the same manner.
【００３１】放冷しながら２時間攪拌した後に、溶媒を
留去し、固形物を形成した。固形物は、微粒子にＰＶＡ
またはＰＡＡのポリマーが被覆されて構成されている。
微粒子の合金組成はａｔ％でＰｄ−Ｐｔ合金であり、ａ
ｔ％でＰｄ：Ｐｔ=８０：２０であった。その固形物を
所定の溶媒（２−ブトキシエタノール：極性溶媒）に分
散させ、表１に示す４種類の水素吸蔵放出流体（試料Ｅ
〜試料Ｈ）を形成した。この場合、金属量は５ｇであ
り、水素吸蔵放出流体に占める濃度としては１０ｗｔ％
である。この流体５０ｃｍ3を以下のＰＣＴ特性測定に
供した。After stirring for 2 hours while allowing to cool, the solvent was distilled off to form a solid. Solid material is PVA
Alternatively, it is constituted by coating a polymer of PAA.
The alloy composition of the fine particles is a Pd-Pt alloy at at%, and a
At t%, Pd: Pt = 80: 20. The solid was dispersed in a predetermined solvent (2-butoxyethanol: polar solvent), and the four types of hydrogen storage / release fluids shown in Table 1 (sample E) were used.
~ Sample H) was formed. In this case, the amount of metal is 5 g, and the concentration in the hydrogen storage-release fluid is 10 wt%.
It is. 50 cm 3 of this fluid was subjected to the following PCT characteristic measurement.
【００３２】４種類の水素吸蔵放出流体（試料Ｅ〜試料
Ｈ）について、ＰＣＴ特性を試験した。更に、比較例１
で用いた微粒子と同様の微粒子を用意し、これを試料Ｅ
〜試料Ｈと同じ溶媒に同一濃度で分散させ、比較例２の
水素吸蔵放出流体を形成した。比較例２の水素吸蔵放出
流体ついても同様に試験した。図２は試験結果を示す。
図２の横軸はサイクル数を示す、縦軸は水素の最大吸蔵
量［Ｈ／Ｍ］を示す。図２において、◆印は試料Ｅの結
果を示し、■印は試料Ｆを示し、×印は試料Ｇの結果を
示し、□印は試料Ｈを示し、＊印は比較例２を示す。PCT characteristics were tested for four types of hydrogen storage / release fluids (Samples E to H). Further, Comparative Example 1
A fine particle similar to the fine particles used in the above was prepared, and this was used as a sample E
-Dispersed in the same solvent as Sample H at the same concentration to form a hydrogen storage-release fluid of Comparative Example 2. The hydrogen storage / release fluid of Comparative Example 2 was similarly tested. FIG. 2 shows the test results.
The horizontal axis in FIG. 2 indicates the number of cycles, and the vertical axis indicates the maximum hydrogen storage amount [H / M]. In FIG. 2, a mark indicates the result of Sample E, a mark indicates the result of Sample F, a mark indicates the result of Sample G, a mark indicates Sample H, and a mark indicates Comparative Example 2.
【００３３】図２から理解できるように、比較例２の水
素吸蔵放出流体では、サイクル数が増加するにつれて、
最大吸蔵量は次第に低下し、５００サイクル目ではかな
り低下した。これに対して本実施例品に係る試料Ｅ、試
料Ｆ、試料Ｇおよび試料Ｈの各水素吸蔵放出流体では、
サイクル数が増加しても、水素の最大吸蔵量はあまり低
下しなかった。例えばサイクル数が１００サイクル、２
００サイクル、３００サイクル、４００サイクル、５０
０サイクルを越えても、水素の最大吸蔵量はあまり低下
しなかった。As can be understood from FIG. 2, in the hydrogen storage / release fluid of Comparative Example 2, as the number of cycles increases,
The maximum occlusion gradually decreased, and decreased considerably at the 500th cycle. On the other hand, in each of the hydrogen storage / release fluids of Sample E, Sample F, Sample G, and Sample H according to the product of the present embodiment,
As the number of cycles increased, the maximum amount of hydrogen stored did not decrease much. For example, if the number of cycles is 100, 2
00 cycles, 300 cycles, 400 cycles, 50
Even after 0 cycles, the maximum hydrogen storage amount did not decrease so much.
【００３４】試料Ｅ〜試料Ｈの水素吸蔵放出流体につい
てサイクル劣化度、流体安定性を試べた。比較例２の水
素吸蔵放出流体についても同様に試べた。表２は、試料
Ｅ〜試料Ｈおよび比較例２に係る水素吸蔵放出流体の条
件、サイクル劣化度および流体安定性についての試験結
果を示す。表２に示すように、試料Ｅでは、固形物のう
ちＰＶＡ重量は８５ｗｔ％であり、微粒子の平均粒子径
は５ｎｍであり、サイクル劣化度は８５％であり、２週
間以上放置しても水素吸蔵放出流体は安定であり、沈降
は認められなかった。With respect to the hydrogen storage / release fluids of Samples E to H, the cycle deterioration degree and fluid stability were tested. The hydrogen storage / release fluid of Comparative Example 2 was similarly tested. Table 2 shows the test results for the conditions, cycle deterioration degree, and fluid stability of the hydrogen storage / release fluid according to Samples E to H and Comparative Example 2. As shown in Table 2, in Sample E, the PVA weight of the solid was 85 wt%, the average particle diameter of the fine particles was 5 nm, the degree of cycle deterioration was 85%, and hydrogen was observed even when left for two weeks or more. The occluding and releasing fluid was stable and no sedimentation was observed.
【００３５】試料Ｆでは、固形物のうちＰＶＡ重量は６
５ｗｔ％であり、微粒子の平均粒子径は５ｎｍであり、
サイクル劣化度は８０．５％であり、２週間以上放置し
ても水素吸蔵放出流体は安定であった。試料Ｇでは、固
形物のうちＰＡＡ重量は８５ｗｔ％であり、微粒子の平
均粒子径は５ｎｍであり、サイクル劣化度は８４．０％
であり、２週間以上放置しても水素吸蔵放出流体は安定
であった。In sample F, the PVA weight of the solid was 6
5 wt%, the average particle diameter of the fine particles is 5 nm,
The cycle deterioration degree was 80.5%, and the hydrogen storage / release fluid was stable even after standing for 2 weeks or more. In sample G, the weight of the PAA was 85 wt% of the solid, the average particle diameter of the fine particles was 5 nm, and the degree of cycle deterioration was 84.0%.
The hydrogen storage / release fluid was stable even after standing for 2 weeks or more.
【００３６】試料Ｈでは、固形物のうちＰＡＡ重量は６
５ｗｔ％であり、微粒子の平均粒子径は５ｎｍであり、
サイクル劣化度は８３％であり、２週間以上放置しても
水素吸蔵放出流体は安定であった。比較例２では、サイ
クル劣化度は３３．５％でありサイクル劣化性が大き
く、また流体安定性の評価は『×』であり良好ではなか
った。In sample H, the PAA weight of the solid was 6
5 wt%, the average particle diameter of the fine particles is 5 nm,
The degree of cycle deterioration was 83%, and the hydrogen storage / release fluid was stable even after standing for 2 weeks or more. In Comparative Example 2, the cycle deterioration degree was 33.5% and the cycle deterioration property was large, and the evaluation of the fluid stability was “×”, which was not good.
【００３７】上記した試験結果から、本実施例に係る試
料Ｅ〜試料Ｈについては、水素吸蔵操作および水素放出
操作を繰り返しても、水素吸蔵放出流体の劣化は抑制さ
れ、水素吸蔵能の低下を抑制できることがわかる。更に
長期間放置しても、微粒子の沈降を抑制できることがわ
かる。From the above test results, regarding the samples E to H according to the present embodiment, even if the hydrogen storage operation and the hydrogen release operation are repeated, the deterioration of the hydrogen storage and release fluid is suppressed, and the decrease in the hydrogen storage capacity is suppressed. It can be seen that it can be suppressed. It can be seen that the sedimentation of the fine particles can be suppressed even after being left for a long time.
【００３８】[0038]
【表２】 （実施例３）また上記した試料Ｈに係る固形物を用い、
溶媒をエチレングリコール、水、シリコーンオイル（東
レ ＳＨ−２００）に変更し、同様に試験を行った。試
験結果を図３に示す。図３において、■印はエチレング
リコールの結果を示し、×印は水の結果を示し、□印は
シリコーンオイルの結果を示し、また、◆印は実施例２
に係る２−ブトキシエタノールの結果（試料Ｈ）を示
す。[Table 2] (Example 3) Further, using the solid matter according to Sample H described above,
The test was performed in the same manner except that the solvent was changed to ethylene glycol, water, and silicone oil (Toray SH-200). The test results are shown in FIG. In FIG. 3, the mark ■ indicates the result of ethylene glycol, the mark × indicates the result of water, the mark □ indicates the result of silicone oil, and the mark ◆ indicates the result of Example 2.
2 shows the results (sample H) of 2-butoxyethanol.
【００３９】いずれの溶媒を用いた水素吸蔵放出流体に
ついても、水素吸蔵および水素放出を多数サイクル繰り
返したとき、水素の最大吸蔵量はあまり低下せず、サイ
クル劣化性を低減させ得ることができた。即ち、サイク
ル劣化度としては、２−ブトキシエタノールのときには
８３％であり、エチレングリコールのときには８１．５
％であり、水のときには７７．５％であり、シリコーン
オイルのときには７２．５％であった。水素吸蔵放出流
体の流体安定性としては、いずれの溶媒を用いたとき
も、２週間以上放置しても安定であった。Regarding the hydrogen storage and release fluid using any of the solvents, when the hydrogen storage and release were repeated many times, the maximum storage amount of hydrogen did not decrease so much, and the cycle deterioration was able to be reduced. . That is, the cycle deterioration degree is 83% for 2-butoxyethanol and 81.5 for ethylene glycol.
% For water and 72.5% for silicone oil. Regarding the fluid stability of the hydrogen storage and release fluid, when any of the solvents was used, the fluid was stable even after standing for 2 weeks or more.
【００４０】（適用例）図５は適用例を示す。この例
は、水素吸蔵放出流体を用いるシステム装置を示す。水
素吸蔵放出流体を用いるシステム装置は、水素吸蔵放出
流体が収容可能な液体収容室１０をもつ収容容器１と、
収容容器１に設けられた入口通路１１と、収容容器１の
底付近に設けられた出口通路１２と、収容容器１の液体
収容室１０の内部に配置された放出促進手段２とを備え
ている。(Application Example) FIG. 5 shows an application example. This example shows a system device using a hydrogen storage-release fluid. The system device using the hydrogen storage / release fluid includes a storage container 1 having a liquid storage chamber 10 capable of storing the hydrogen storage / release fluid,
The container 1 includes an inlet passage 11 provided in the container 1, an outlet passage 12 provided in the vicinity of the bottom of the container 1, and a discharge promoting unit 2 disposed inside the liquid container 10 of the container 1. .
【００４１】放出促進手段２は、液体収容室１０内の水
素吸蔵放出流体を加熱する加熱手段として機能するもの
であり、加熱に伴い水素吸蔵放出流体からの水素の放出
を促進するものである。放出促進手段２は、加熱水が流
れるため水素吸蔵放出流体と熱交換する熱交換器として
機能できる加熱管２０と、加熱管２０に加熱水を送給す
る加熱水生成送給装置２２とをもつ。The release promoting means 2 functions as a heating means for heating the hydrogen storage and release fluid in the liquid storage chamber 10, and promotes the release of hydrogen from the hydrogen storage and release fluid with heating. The release promoting means 2 has a heating pipe 20 that can function as a heat exchanger that exchanges heat with the hydrogen storage / release fluid because the heated water flows, and a heated water generation / supply device 22 that supplies heated water to the heating pipe 20. .
【００４２】加熱水生成送給装置２２は、加熱水を送給
するポンプ２３と、高温水を送給する高温水供給部２４
と、高温水より低温の水を送給する冷水供給部２５とを
もつ。冷水供給部２５からの冷水と高温水供給部２４か
らの高温水とが混合され、これにより所定の温度領域を
もつように温度調整された加熱水（例えば５０〜１００
℃）が形成され、この加熱水が加熱管２０に送給され
る。The heating water generating / sending device 22 includes a pump 23 for feeding heating water, and a high-temperature water feeding unit 24 for feeding high-temperature water.
And a cold water supply unit 25 for supplying water lower in temperature than hot water. The cold water from the cold water supply unit 25 and the high-temperature water from the high-temperature water supply unit 24 are mixed, so that the temperature of the heated water (for example, 50 to 100) is adjusted to have a predetermined temperature range.
C) is formed, and the heated water is supplied to the heating tube 20.
【００４３】冷水供給部２５からの冷水と高温水供給部
２４からの高温水とが混合される割合により、加熱水の
温度が調整される。これにより単位時間における水素放
出率が調整される。従って、加熱水生成送給装置２２は
加熱水の水温調整機能をもつ。入口通路１１を開閉する
ための開閉弁１１ａが開放されると、入口通路１１から
水素吸蔵放出流体が液体収容室１０に送給される。液体
収容室１０に水素吸蔵放出流体が収容されている状態
で、放出促進手段２の加熱管２０に加熱水が送給される
と、加熱水の熱は収容容器１内の水素吸蔵放出流体に伝
達され、水素吸蔵放出流体が加熱される。これにより水
素吸蔵放出流体から水素が放出される。放出された水素
は、ガス出口通路１３、開放状態の開閉弁１３ａを経て
水素消費部１５（例えば水素エンジン、燃料電池）に送
給される。The temperature of the heated water is adjusted by the mixing ratio of the cold water from the cold water supply unit 25 and the high temperature water from the high temperature water supply unit 24. Thereby, the hydrogen release rate per unit time is adjusted. Therefore, the heating water generation and delivery device 22 has a function of adjusting the temperature of the heating water. When the on-off valve 11 a for opening and closing the inlet passage 11 is opened, the hydrogen storage / release fluid is supplied from the inlet passage 11 to the liquid storage chamber 10. When heating water is supplied to the heating pipe 20 of the release promoting means 2 in a state where the hydrogen storage / release fluid is stored in the liquid storage chamber 10, the heat of the heating water is transferred to the hydrogen storage / release fluid in the storage container 1. The transmitted and heated hydrogen storage and release fluid is heated. As a result, hydrogen is released from the hydrogen storage / release fluid. The released hydrogen is supplied to the hydrogen consuming unit 15 (for example, a hydrogen engine or a fuel cell) via the gas outlet passage 13 and the open / close valve 13a.
【００４４】収容容器１内で水素の放出が完了したら、
開閉弁１２ａを開放する。そして水素を放出した後の水
素吸蔵放出流体を出口通路１２から吸蔵部３に送給す
る。吸蔵部３で水素吸蔵放出流体に水素を吸蔵する。吸
蔵部３は、容器３０と、容器３０内に貯留された水素吸
蔵放出流体に浸漬された水素吹出管３２とをもつ。水素
吹出管３２から容器３０内の水素吸蔵放出流体内に吹き
出された水素ガスによりバブリングが発生する。これに
より水素吸蔵放出流体における微粒子と微粒子を覆って
いるポリマーとの相対変位を期待できる。これにより微
粒子への水素の吸蔵が促進されると推察される。水素を
吸蔵した水素吸蔵放出流体は、ポンプ３４により貯蔵タ
ンク４に送給される。When the release of hydrogen in the storage container 1 is completed,
The on-off valve 12a is opened. Then, the hydrogen storage / release fluid after releasing hydrogen is supplied to the storage unit 3 from the outlet passage 12. The storage unit 3 stores hydrogen in the hydrogen storage and release fluid. The storage unit 3 has a container 30 and a hydrogen blowing pipe 32 immersed in a hydrogen storage / release fluid stored in the container 30. Bubbling is generated by the hydrogen gas blown out of the hydrogen blowing pipe 32 into the hydrogen storage / release fluid in the container 30. Thereby, relative displacement between the fine particles in the hydrogen storage / release fluid and the polymer covering the fine particles can be expected. This is presumed to promote the absorption of hydrogen into the fine particles. The hydrogen storage / release fluid storing the hydrogen is supplied to the storage tank 4 by the pump 34.
【００４５】貯蔵タンク４内で水素吸蔵放出流体は貯蔵
される。貯蔵タンク４内の水素吸蔵放出流体は、必要に
応じてポンプ４０により、開放状態の開閉弁１１ａ、入
口通路１１を経て収容容器１に送給される。この水素吸
蔵放出流体は、再び、水素放出に利用できる。 （付記）上記した記載から次の技術的思想も把握でき
る。 ・請求項１において、水素吸蔵および水素放出を１サイ
クルとし、５００サイクル繰り返したとき、サイクル劣
化度が４０％以上、５０％以上,６０％以上,７０％以
上,８０％以上のいずれかであることを特徴とする水素
吸蔵放出流体。 ・請求項１において、微粒子の組成はパラジウム系（例
えばＰｄ−Ａｇ系，Ｐｄ−Ｐｔ系）であることを特徴と
する水素吸蔵放出流体。 ・請求項１において、微粒子の平均粒子径は０．５ｎｍ
〜２０ｎｍあるいは１ｎｍ〜２０ｎｍであることを特徴
とする水素吸蔵放出流体。 ・水素吸蔵能および水素放出能をもつ微粒子となる物質
（Ｐｄ等）を含む溶液と、第１溶媒（水、アルコールな
ど）と、沈降抑制物質となるポリマーとを混合した混合
溶液を形成する工程と、混合溶液から微粒子を生成する
工程と、混合溶液中の溶媒を除去（例えば留去）し、微
粒子にポリマーが被覆されて複合化された固形物を生成
する工程と、固形物を第２溶媒に分散させて水素吸蔵放
出流体を形成する工程とを順に実施することを特徴とす
る水素吸蔵放出流体の製造方法。平均粒子径が極めて小
さい微粒子にポリマーを複合化するのに有利となる。 ・水素吸蔵放出流体が収容可能な液体収容室をもつ収容
容器と、収容容器の液体収容室の内部に配置され水素吸
蔵放出流体の水素放出を促進させる放出促進手段とを備
えていることを特徴とする水素吸蔵放出流体を用いるシ
ステム装置。液体収容室の内部に放出促進手段が配置さ
れているため、水素放出の効率が良好となる。The hydrogen storage / release fluid is stored in the storage tank 4. The hydrogen storage / release fluid in the storage tank 4 is supplied to the storage container 1 by the pump 40 through the open / close valve 11 a and the inlet passage 11 as needed. This hydrogen storage / release fluid can be used again for hydrogen release. (Supplementary Note) The following technical ideas can be understood from the above description. -In claim 1, when 500 cycles are performed with hydrogen absorption and hydrogen release as one cycle, the cycle deterioration degree is any one of 40% or more, 50% or more, 60% or more, 70% or more, and 80% or more. A hydrogen storage / release fluid characterized by the above-mentioned. -The hydrogen storage / release fluid according to claim 1, wherein the composition of the fine particles is a palladium-based (for example, Pd-Ag-based, Pd-Pt-based). -In claim 1, the average particle diameter of the fine particles is 0.5 nm.
Hydrogen storage / release fluid characterized by having a thickness of 20 nm or 1 nm to 20 nm. A step of forming a mixed solution in which a solution containing a substance (Pd or the like) that becomes fine particles having a hydrogen storage ability and a hydrogen releasing ability, a first solvent (water, alcohol, or the like), and a polymer serving as a precipitation-preventing substance are mixed; A step of generating fine particles from the mixed solution, a step of removing (e.g., distilling off) the solvent in the mixed solution, and forming a solid material in which the polymer is coated on the fine particles to form a composite material; Forming a hydrogen storage and release fluid by dispersing in a solvent. This is advantageous for compounding a polymer with fine particles having an extremely small average particle diameter. A storage container having a liquid storage chamber capable of storing the hydrogen storage and release fluid; and a release promoting means disposed inside the liquid storage chamber of the storage container to promote the release of the hydrogen storage and release fluid from hydrogen. A system device using a hydrogen storage / release fluid. Since the release promoting means is disposed inside the liquid storage chamber, the efficiency of releasing hydrogen is improved.
【００４６】[0046]
【発明の効果】本発明の水素吸蔵放出流体によれば、放
置時間が長くなっても、微粒子の沈降を抑制できる。更
に微粒子の酸化等の被毒を抑制でき、水素吸蔵および水
素放出を多数サイクル繰り返したとしても、サイクル劣
化性を低減させるのに有利となる。故に水素吸蔵放出流
体の目標性能を得るのに有利である。According to the hydrogen storage / release fluid of the present invention, sedimentation of fine particles can be suppressed even when the storage time is long. Further, poisoning such as oxidation of the fine particles can be suppressed, which is advantageous for reducing cycle deterioration even if hydrogen storage and hydrogen release are repeated many times. Therefore, it is advantageous for obtaining the target performance of the hydrogen storage / release fluid.
【図１】実施例１に係る試験結果を示すグラフである。FIG. 1 is a graph showing test results according to Example 1.
【図２】実施例２に係る試験結果を示すグラフである。FIG. 2 is a graph showing test results according to Example 2.
【図３】実施例２に係る試験結果を示すグラフである。FIG. 3 is a graph showing test results according to Example 2.
【図４】水素吸蔵放出流体の微粒子付近を模式的に示す
概念図である。FIG. 4 is a conceptual diagram schematically showing the vicinity of fine particles of a hydrogen storage / release fluid.
【図５】適用例に係る構成図である。FIG. 5 is a configuration diagram according to an application example.
図中、１は収容容器、１０は流体収容室、２は放出促進
手段、１００は微粒子、２００はポリマーを示す。In the figure, 1 is a storage container, 10 is a fluid storage chamber, 2 is a release promoting means, 100 is fine particles, and 200 is a polymer.
Claims (1)
子を溶媒中に分散させると共に、前記微粒子の沈降を抑
える沈降抑制物質が含まれていることを特徴とする水素
吸蔵放出流体。1. A hydrogen storage and release fluid comprising fine particles having a hydrogen storage ability and a hydrogen release ability dispersed in a solvent, and a sedimentation-suppressing substance for suppressing the sedimentation of the fine particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11162599A JP2000351603A (en) | 1999-06-09 | 1999-06-09 | Hydrogen absorbing and desorbing fluid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11162599A JP2000351603A (en) | 1999-06-09 | 1999-06-09 | Hydrogen absorbing and desorbing fluid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000351603A true JP2000351603A (en) | 2000-12-19 |
Family
ID=15757664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11162599A Pending JP2000351603A (en) | 1999-06-09 | 1999-06-09 | Hydrogen absorbing and desorbing fluid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000351603A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014527119A (en) * | 2011-06-08 | 2014-10-09 | ユナイテッド テクノロジーズ コーポレイション | Removal of surfactant from palladium nanoparticles |
-
1999
- 1999-06-09 JP JP11162599A patent/JP2000351603A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014527119A (en) * | 2011-06-08 | 2014-10-09 | ユナイテッド テクノロジーズ コーポレイション | Removal of surfactant from palladium nanoparticles |
| US9553318B2 (en) | 2011-06-08 | 2017-01-24 | Audi Ag | Surfactant removal from palladium nanoparticles |
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