JP4793900B2 - Hydrogen storage material and method for producing the same - Google Patents
Hydrogen storage material and method for producing the same Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 147
- 239000001257 hydrogen Substances 0.000 title claims description 121
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 121
- 239000011232 storage material Substances 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 84
- 239000002184 metal Substances 0.000 claims description 84
- -1 amide compound Chemical class 0.000 claims description 75
- 239000003054 catalyst Substances 0.000 claims description 73
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 50
- 239000002105 nanoparticle Substances 0.000 claims description 49
- 229910052987 metal hydride Inorganic materials 0.000 claims description 44
- 150000004681 metal hydrides Chemical class 0.000 claims description 44
- 239000011261 inert gas Substances 0.000 claims description 38
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 31
- 239000011777 magnesium Substances 0.000 claims description 29
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 26
- 238000010298 pulverizing process Methods 0.000 claims description 26
- PKMBLJNMKINMSK-UHFFFAOYSA-N magnesium;azanide Chemical compound [NH2-].[NH2-].[Mg+2] PKMBLJNMKINMSK-UHFFFAOYSA-N 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 23
- 229910052749 magnesium Inorganic materials 0.000 claims description 23
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 14
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- 238000007670 refining Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 4
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 4
- 150000001408 amides Chemical class 0.000 claims 4
- 230000002708 enhancing effect Effects 0.000 claims 1
- 150000004678 hydrides Chemical class 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000003860 storage Methods 0.000 description 22
- 229910052786 argon Inorganic materials 0.000 description 21
- 239000000463 material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000000446 fuel Substances 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000011859 microparticle Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910017958 MgNH Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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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
- Y02E60/50—Fuel cells
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- Fuel Cell (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Hydrogen, Water And Hydrids (AREA)
Description
本発明は、燃料電池等の燃料として用いられる水素貯蔵材料およびその製造方法に関する。 The present invention relates to a hydrogen storage material used as a fuel for fuel cells and the like, and a method for producing the same.
ＮＯＸやＳＯＸ等の有害物質やＣＯ２等の温室効果ガスを出さないクリーンなエネルギー源として燃料電池の開発が盛んに行われており、既に幾つかの分野で実用化されている。この燃料電池技術を支える重要な技術として、燃料電池の燃料となる水素を貯蔵する技術がある。水素の貯蔵形態としては、高圧ボンベによる圧縮貯蔵や液体水素化させる冷却貯蔵、水素貯蔵物質による貯蔵が知られており、これらの形態の中で、水素貯蔵物質による貯蔵は、分散貯蔵や輸送の点で有利である。水素貯蔵物質としては、水素貯蔵効率の高い材料、つまり水素貯蔵物質の単位重量または単位体積あたりの水素貯蔵量が高い材料、低い温度で水素の吸収／放出が行われる材料、良好な耐久性を有する材料が望まれる。 NO X and development of fuel cells have been actively as a clean energy source that does not emit greenhouse gases such as toxic substances and CO 2 in the SO X or the like, and is already practiced in several areas. As an important technology that supports this fuel cell technology, there is a technology for storing hydrogen as fuel for the fuel cell. As storage forms of hydrogen, compression storage by high-pressure cylinders, cooling storage by liquid hydrogenation, and storage by hydrogen storage materials are known. Among these forms, storage by hydrogen storage materials is used for distributed storage and transportation. This is advantageous. Hydrogen storage materials include materials with high hydrogen storage efficiency, that is, materials with a high hydrogen storage amount per unit weight or volume of the hydrogen storage material, materials that absorb / release hydrogen at a low temperature, and good durability. A material having is desired.
従来、水素貯蔵物質としては、希土類系、チタン系、バナジウム系、マグネシウム系等を中心とする金属材料、金属アラネート（例えば、ＮａＡｌＨ４やＬｉＡｌＨ４）等の軽量無機化合物、カーボン等の種々の材料が知られている。また、例えば、下式（１）で示されるリチウム窒化物を用いた水素貯蔵方法も報告されている（例えば、非特許文献１、２参照）。
Ｌｉ３Ｎ＋２Ｈ２⇔Ｌｉ２ＮＨ＋ＬｉＨ＋Ｈ２⇔ＬｉＮＨ２＋２ＬｉＨ…（１）
Conventionally, as a hydrogen storage material, various materials such as metal materials such as rare earth, titanium, vanadium, and magnesium, lightweight inorganic compounds such as metal alanate (for example, NaAlH 4 and LiAlH 4 ), and carbon, etc. It has been known. In addition, for example, a hydrogen storage method using lithium nitride represented by the following formula (1) has been reported (for example, see Non-Patent Documents 1 and 2).
Li 3 N + 2H 2 ⇔Li 2 NH + LiH + H 2 ⇔LiNH 2 + 2LiH (1)
ここで、Ｌｉ３Ｎによる水素の吸収は１００℃程度から開始し、２５５℃、３０分で９．３質量％の水素吸収が確認されている。また、吸収された水素の放出特性としては、ゆっくり加熱することによって２００℃弱で６．３質量％、３２０℃以上で３．０質量％と、二段階のステップを経ることが報告されている。すなわち、上記（１）式の右辺部分に相当する下式（２）の反応は２００℃弱で進行し始め、上記（１）式の左辺部分に相当する下式（３）の反応は約３２０℃で進行し始めることが示されている。
ＬｉＮＨ２＋２ＬｉＨ→Ｌｉ２ＮＨ＋ＬｉＨ＋Ｈ２↑…（２）
Ｌｉ２ＮＨ＋ＬｉＨ→Ｌｉ３Ｎ＋Ｈ２↑…（３）
Here, absorption of hydrogen by Li 3 N started from about 100 ° C., and 9.3 mass% hydrogen absorption was confirmed at 255 ° C. for 30 minutes. In addition, it has been reported that the absorption characteristics of absorbed hydrogen pass through two steps: 6.3% by mass at less than 200 ° C. and 3.0% by mass at 320 ° C. or higher by slowly heating. . That is, the reaction of the following formula (2) corresponding to the right side portion of the above formula (1) starts to proceed at a little less than 200 ° C., and the reaction of the following formula (3) corresponding to the left side portion of the above formula (1) is about 320 It has been shown to begin to progress at ° C.
LiNH 2 + 2LiH → Li 2 NH + LiH + H 2 ↑ (2)
Li 2 NH + LiH → Li 3 N + H 2 ↑ (3)
しかしながら、上記（１）式に示されるリチウム窒化物は、水素放出温度が高いという問題がある。
発明者らはかかる事情に鑑み、先に特願２００３−２９１６７２号において、リチウムアミド（ＬｉＮＨ２）と水素化リチウム（ＬｉＨ）をナノ構造化することにより、水素発生反応温度を低温側へシフトさせた水素貯蔵材料を開示した。しかし、水素発生反応温度をさらに低温化させることが望まれている。
本発明はかかる事情に鑑みてなされたものであり、水素放出温度を低温化させた水素貯蔵材料、およびその製造方法を提供することを目的とする。
In view of such circumstances, the inventors previously made a nanostructure of lithium amide (LiNH 2 ) and lithium hydride (LiH) in Japanese Patent Application No. 2003-291672 to shift the hydrogen generation reaction temperature to the low temperature side. A hydrogen storage material has been disclosed. However, it is desired to further lower the hydrogen generation reaction temperature.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a hydrogen storage material having a reduced hydrogen release temperature and a method for producing the same.
本発明の第１の観点によれば、金属水素化物と金属アミド化合物と水素吸放出能を高める触媒とを含む混合物または複合化物から構成される水素貯蔵材料であって、前記触媒はＴｉＯ ２ ナノ粒子またはＴｉナノ粒子からなり、前記金属水素化物と金属アミド化合物の金属種が２種であって、金属種はリチウムおよびマグネシウムであることを特徴とする水素貯蔵材料、が提供される。 According to a first aspect of the present invention, there is provided a hydrogen storage material comprising a mixture or composite comprising a metal hydride, a metal amide compound, and a catalyst that enhances hydrogen absorption / release capability, the catalyst comprising TiO 2 nano Ri particles or Ti nanoparticles Tona, wherein a metal species two metal hydride and a metal amide compound, hydrogen storage material metal species, which is a lithium and magnesium, are provided.
この水素貯蔵材料において、好ましい組み合わせとして、前記金属水素化物が水素化リチウムであり、前記金属アミド化合物がマグネシウムアミドである組み合わせが挙げられ、この場合には、マグネシウムアミド１モルに対する水素化リチウムの混合比を２モル以上５モル以下とすることが好ましい。別の好ましい組み合わせとしては、前記金属水素化物が水素化マグネシウムであり、前記金属アミド化合物がリチウムアミドである組み合わせが挙げられ、この場合には、リチウムアミド１モルに対する水素化マグネシウムの混合比を０．５モル以上３モル以下とすることが好ましい。触媒の担持量は、金属水素化物と金属アミド化合物との混合物または複合化物の合計量の０．１質量％以上２０質量％以下とすることが好ましい。 In this hydrogen storage material , a preferable combination includes a combination in which the metal hydride is lithium hydride and the metal amide compound is magnesium amide . In this case, a mixture of lithium hydride with respect to 1 mol of magnesium amide is used. The ratio is preferably 2 mol or more and 5 mol or less. Another preferred combination is a combination in which the metal hydride is magnesium hydride and the metal amide compound is lithium amide . In this case, the mixing ratio of magnesium hydride to 1 mol of lithium amide is 0. It is preferably 5 mol or more and 3 mol or less. The supported amount of the catalyst is preferably 0.1% by mass or more and 20% by mass or less of the total amount of the mixture or composite of the metal hydride and the metal amide compound.
本発明の第２の観点によれば、金属水素化物と金属アミド化合物と水素吸放出能を高める触媒とを含む混合物または複合化物から構成され、前記触媒はＴｉＯ ２ ナノ粒子またはＴｉナノ粒子からなり、前記金属水素化物と金属アミド化合物の金属種が２種であって、金属種はリチウムおよびマグネシウムである水素貯蔵材料の製造方法であって、
前記金属水素化物と前記金属アミド化合物に、前記触媒を添加して、不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下において機械的粉砕処理により混合、微細化することを特徴とする水素貯蔵材料の製造方法、が提供される。
According to a second aspect of the present invention, the catalyst is composed of a mixture or composite comprising a metal hydride, a metal amide compound, and a catalyst that enhances hydrogen absorption / release capability, and the catalyst is composed of TiO 2 nanoparticles or Ti nanoparticles. A method for producing a hydrogen storage material, wherein the metal hydride and the metal amide compound have two metal species, and the metal species are lithium and magnesium,
To the metal hydride and the metal amide compound with the addition of the catalyst, mixing by mechanical pulverization treatment in a mixed gas atmosphere of an inert gas atmosphere or hydrogen gas atmosphere or an inert gas and hydrogen gas, fine A method for producing a hydrogen storage material is provided.
本発明の第３の観点によれば、金属水素化物と金属アミド化合物と水素吸放出能を高める触媒とを含む混合物または複合化物から構成され、前記触媒はＴｉＯ ２ ナノ粒子またはＴｉナノ粒子からなり、前記金属水素化物と金属アミド化合物の金属種が２種であって、金属種はリチウムおよびマグネシウムである水素貯蔵材料の製造方法であって、
前記金属水素化物と前記金属アミド化合物を不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下において機械的粉砕処理により混合、微細化する第１工程と、
前記第１工程により得られた被処理物に、前記触媒を添加して、前記被処理物に前記触媒を担持させる第２工程と、
を有することを特徴とする水素貯蔵材料の製造方法、が提供される。
According to a third aspect of the present invention, the catalyst is composed of a mixture or composite comprising a metal hydride, a metal amide compound, and a catalyst that enhances hydrogen absorption / release capability, the catalyst comprising TiO 2 nanoparticles or Ti nanoparticles. A method for producing a hydrogen storage material, wherein the metal hydride and the metal amide compound have two metal species, and the metal species are lithium and magnesium,
Mixed by mechanical pulverization treatment under a mixed gas atmosphere of said metal hydride with said metal amide compound an inert gas atmosphere or hydrogen gas atmosphere or an inert gas and hydrogen gas, a first step of refining,
A second step of adding the catalyst to the object to be processed obtained in the first step and loading the catalyst on the object to be processed;
A method for producing a hydrogen storage material is provided.
本発明の第４の観点によれば、金属水素化物と金属アミド化合物と水素吸放出能を高める触媒とを含む混合物または複合化物から構成され、前記触媒はＴｉＯ ２ ナノ粒子またはＴｉナノ粒子からなり、前記金属水素化物と金属アミド化合物の金属種が２種であって、金属種はリチウムおよびマグネシウムである水素貯蔵材料の製造方法であって、
前記金属水素化物または前記金属アミド化合物のいずれか一方に、前記触媒を添加して、不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下において、機械的粉砕処理により混合、微細化する第１工程と、
前記第１工程により得られた被処理物と他方とを、不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下において、混合粉砕する工程と、
を有することを特徴とする水素貯蔵材料の製造方法、が提供される。
According to a fourth aspect of the present invention, the catalyst comprises a mixture or composite comprising a metal hydride, a metal amide compound, and a catalyst that enhances hydrogen absorption / release capability, and the catalyst comprises TiO 2 nanoparticles or Ti nanoparticles. A method for producing a hydrogen storage material, wherein the metal hydride and the metal amide compound have two metal species, and the metal species are lithium and magnesium,
Any one of the metal hydride or the metal amide compound with the addition of the catalyst, a mixed gas atmosphere of an inert gas atmosphere or hydrogen gas atmosphere or an inert gas and hydrogen gas, mechanical pulverization A first step of mixing and refining by processing;
Mixing and pulverizing the object to be processed and the other obtained in the first step under an inert gas atmosphere or a hydrogen gas atmosphere or a mixed gas atmosphere of an inert gas and hydrogen gas;
A method for producing a hydrogen storage material is provided.
本発明の第５の観点によれば、金属水素化物と金属アミド化合物と水素吸放出能を高める触媒とを含む混合物または複合化物から構成され、前記触媒はＴｉＯ ２ ナノ粒子またはＴｉナノ粒子からなり、前記金属水素化物と金属アミド化合物の金属種が２種であって、金属種はリチウムおよびマグネシウムである水素貯蔵材料の製造方法であって、
前記金属水素化物と前記金属アミド化合物それぞれに、前記触媒を添加して、前記金属水素化物と金属アミド化合物ごとに、不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下において、機械的粉砕処理により混合、微細化する第１工程と、
前記第１工程により得られた被処理物どうしを、不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下において、混合粉砕する第２工程と、
を有することを特徴とする水素貯蔵材料の製造方法、が提供される。
According to a fifth aspect of the present invention, the catalyst is composed of a mixture or composite comprising a metal hydride, a metal amide compound, and a catalyst that enhances hydrogen absorption / release capability, and the catalyst is composed of TiO 2 nanoparticles or Ti nanoparticles. A method for producing a hydrogen storage material, wherein the metal hydride and the metal amide compound have two metal species, and the metal species are lithium and magnesium,
Each said metal hydride with said metal amide compound with the addition of the catalyst, mixing with the per metal hydride and a metal amide compound, under an inert gas atmosphere or under a hydrogen gas atmosphere or an inert gas and hydrogen gas A first step of mixing and refining by a mechanical pulverization process in a gas atmosphere;
A second step of mixing and grinding the objects to be processed obtained in the first step under an inert gas atmosphere or a hydrogen gas atmosphere or a mixed gas atmosphere of an inert gas and hydrogen gas;
A method for producing a hydrogen storage material is provided.
本発明の水素貯蔵材料によれば、従来よりも水素放出温度を低温化させることができる。これにより、水素貯蔵材料から水素を放出させるための加熱に要するエネルギーを低減させ、また、水素貯蔵材料を充填する容器等の材質や構造の制限が緩和されるようになる。 According to the hydrogen storage material of the present invention, the hydrogen release temperature can be lowered as compared with the conventional case. As a result, the energy required for heating to release hydrogen from the hydrogen storage material is reduced, and restrictions on the material and structure of the container and the like filled with the hydrogen storage material are relaxed.
本発明に係る第１の材料系は、金属水素化物と金属アミド化合物と水素吸放出能を高める触媒とを含む混合物または複合化物から構成される水素貯蔵材料であり、ここで、触媒としてはナノ粒子からなるもの（以下、「ナノ粒子触媒」という）を用いる。ナノ粒子触媒を水素貯蔵材料に担持させることにより、水素放出温度を低温化させることができる。 A first material system according to the present invention is a hydrogen storage material composed of a mixture or a composite containing a metal hydride, a metal amide compound, and a catalyst that enhances hydrogen absorption / release capability. What consists of particle | grains (henceforth "nanoparticle catalyst") is used. By supporting the nanoparticle catalyst on the hydrogen storage material, the hydrogen release temperature can be lowered.
一般的に、ナノ粒子とは粒径が実質的にサブミクロンオーダー未満の粒子を言うが、本発明におけるナノ粒子触媒とは、この一般的な定義に加えて、所定の水素貯蔵材料へ添加した場合に、そのナノ粒子触媒と同組成のマイクロ粒子触媒を同添加率で水素貯蔵材料に添加した場合よりも、水素放出スペクトルのピーク温度（以下「水素放出温度」という）を１０℃以上低下させる効果を示すものを指すものとする。なお、マイクロ粒子触媒とは、平均粒子径が０．５μｍ以上３０μｍ以下であるか、または粒子数の９割以上が０．１μｍ以上１００μｍ以下の範囲にある粒子、または、ＢＥＴ比表面積が１．０ｍ２／ｇ超２０ｍ２／ｇ未満の粒子を指すものとする。 In general, a nanoparticle means a particle having a particle size substantially less than submicron order. In addition to the general definition, the nanoparticle catalyst in the present invention is added to a predetermined hydrogen storage material. In some cases, the peak temperature of the hydrogen release spectrum (hereinafter referred to as “hydrogen release temperature”) is lowered by 10 ° C. or more, compared with the case where a microparticle catalyst having the same composition as the nanoparticle catalyst is added to the hydrogen storage material at the same addition rate. It shall indicate an effect. The microparticle catalyst is a particle having an average particle diameter of 0.5 μm or more and 30 μm or less, or 90% or more of the number of particles in a range of 0.1 μm or more and 100 μm or less, or a BET specific surface area of 1. It is intended to refer to 0 m 2 / g ultra 20 m 2 / g particles less than.
金属水素化物と金属アミド化合物の金属種としては、リチウム、マグネシウム、カルシウムのいずれかが好適に用いられ、水素放出温度を低温化させる観点からは、これら金属水素化物と金属アミド化合物の金属種を２種類以上とすることが好ましい。 As the metal species of the metal hydride and the metal amide compound, any of lithium, magnesium and calcium is preferably used. From the viewpoint of lowering the hydrogen release temperature, the metal species of the metal hydride and the metal amide compound are selected. Two or more types are preferable.
特に好ましい組み合わせとして、水素化リチウムとマグネシウムアミドの組み合わせが挙げられる。水素化リチウムとマグネシウムアミドとの水素放出反応は、下記（４）式および下記（５）式で表される。
２ＬｉＨ＋Ｍｇ（ＮＨ２）２⇔Ｌｉ２ＮＨ＋ＭｇＮＨ＋２Ｈ２ …（４）
８ＬｉＨ＋３Ｍｇ（ＮＨ２）２⇔４Ｌｉ２ＮＨ＋Ｍｇ３Ｎ２＋８Ｈ２ …（５）
A particularly preferred combination is a combination of lithium hydride and magnesium amide. The hydrogen releasing reaction between lithium hydride and magnesium amide is represented by the following formula (4) and the following formula (5).
2LiH + Mg (NH 2 ) 2 ⇔Li 2 NH + MgNH + 2H 2 (4)
8LiH + 3Mg (NH 2 ) 2 ⇔4Li 2 NH + Mg 3 N 2 + 8H 2 (5)
上記（４）式および（５）式を考察すると、上記（４）式では、１モルのマグネシウムアミドに対して２モルの水素化リチウムが化学等量であり、理論水素貯蔵率は５．４８質量％となる。一方、上記（５）式では、１モルのマグネシウムアミドに対して２．６７モルの水素化リチウムが化学等量であり、理論水素貯蔵率は６．８５質量％となる。したがって、マグネシウムアミドと水素化リチウムの組成比が変化することで支配的に起こる反応が変わり、また水素貯蔵率も変わってくることになる。 Considering the above formulas (4) and (5), in the above formula (4), 2 mol of lithium hydride is equivalent to 1 mol of magnesium amide, and the theoretical hydrogen storage rate is 5.48. It becomes mass%. On the other hand, in the above formula (5), 2.67 mol of lithium hydride is a chemical equivalent with respect to 1 mol of magnesium amide, and the theoretical hydrogen storage rate is 6.85 mass%. Therefore, the reaction that occurs predominantly changes as the composition ratio of magnesium amide and lithium hydride changes, and the hydrogen storage rate also changes.
ここで、上記（５）式を下記（６ａ）式および（６ｂ）式に分けて考える。
６ＬｉＨ＋３Ｍｇ（ＮＨ２）２⇔３Ｌｉ２ＮＨ＋３ＭｇＮＨ＋６Ｈ２ …（６ａ）
３ＭｇＮＨ＋２ＬｉＨ⇔Ｌｉ２ＮＨ＋Ｍｇ３Ｎ２＋２Ｈ２ …（６ｂ）
すると、上記（６ａ）式は上記（４）式における各物質の係数を３倍したものであり、実質的に上記（４）式と同じである。そして、上記（６ｂ）式は上記（６ａ）式で生成したマグネシウムイミド（ＭｇＮＨ）と水素化リチウムとの反応である。
Here, the above equation (5) is divided into the following equations (6a) and (6b).
6LiH + 3Mg (NH 2 ) 2 ⇔3Li 2 NH + 3MgNH + 6H 2 (6a)
3MgNH + 2LiH⇔Li 2 NH + Mg 3 N 2 + 2H 2 ... (6b)
Then, the above equation (6a) is obtained by multiplying the coefficient of each substance in the above equation (4) by three, and is substantially the same as the above equation (4). The above formula (6b) is a reaction between magnesium imide (MgNH) produced by the above formula (6a) and lithium hydride.
つまり上記（５）式は、上記（４）式の反応を起こさせようとして水素化リチウムをマグネシウムアミドに対して化学量論比よりも過剰にすると、結果的に、生成したマグネシウムイミドの一部が過剰に添加された水素化リチウムと反応し、窒化マグネシウムが生成するところまで反応が進行する、ということを示している。 In other words, the above formula (5) shows that when lithium hydride is made to exceed the stoichiometric ratio with respect to magnesium amide in order to cause the reaction of the above formula (4), a part of the produced magnesium imide is obtained. Shows that the reaction proceeds to the point where magnesium nitride is formed by reacting with excessively added lithium hydride.
これらのことから、１モルのマグネシウムアミドに対する水素化リチウムの混合比が２未満の場合は、マグネシウムアミドが水素化リチウムに対して過剰であるから、このときには上記（４）式が支配的に進行する。また、１モルのマグネシウムアミドに対する水素化リチウムの混合比が化学量論比である２の場合にも、上記（４）式が支配的に進行する。しかしながら、マグネシウムアミドに対する水素化リチウムの混合比を上記（４）式に合わせたとしても、実際には、マグネシウムイミドと水素化リチウムの混合状態（分散状態）等に依存して、生成したマグネシウムイミドと水素化リチウムとが反応して上記（５）式の反応が進行し、一部のマグネシウムアミドは反応せずに残存することも起こり得ると考えられる。 From these facts, when the mixing ratio of lithium hydride to 1 mol of magnesium amide is less than 2, magnesium amide is excessive with respect to lithium hydride. To do. In addition, when the mixing ratio of lithium hydride to 1 mol of magnesium amide is 2 which is a stoichiometric ratio, the above formula (4) proceeds predominantly. However, even if the mixing ratio of lithium hydride to magnesium amide is adjusted to the above formula (4), the generated magnesium imide actually depends on the mixed state (dispersed state) of magnesium imide and lithium hydride. It is considered that the reaction of the above formula (5) proceeds with the reaction of lithium hydride with some magnesium amide remaining without reacting.
これに対して、１モルのマグネシウムアミドに対する水素化リチウムの混合比が２超２．６７未満の場合は、上記（４）式からみるとマグネシウムアミドに対して水素化リチウムは過剰であるが、上記（５）式からみるとマグネシウムアミドに対して水素化リチウムが不足している。この場合には、混合比が２に近い場合には上記（４）式が支配的に進行して、生成したマグネシウムイミドの一部が窒化マグネシウムへ変化し、混合比が２．６７へ上がるにつれて上記（５）式が支配的に進行するようになる。そして、１モルのマグネシウムアミドに対する水素化リチウムの混合比が２．６７の化学量論比である場合と混合比が２．６７超の場合には、上記（５）式が支配的に進行する。 On the other hand, when the mixing ratio of lithium hydride to 1 mol of magnesium amide is more than 2 and less than 2.67, lithium hydride is excessive with respect to magnesium amide according to the above formula (4). From the above formula (5), lithium hydride is insufficient with respect to magnesium amide. In this case, when the mixing ratio is close to 2, the above formula (4) proceeds predominantly, and part of the generated magnesium imide changes to magnesium nitride, and as the mixing ratio increases to 2.67. The above formula (5) proceeds dominantly. When the mixing ratio of lithium hydride to 1 mol of magnesium amide is a stoichiometric ratio of 2.67 and when the mixing ratio is more than 2.67, the above formula (5) proceeds predominantly. .
これら上記（４）式と上記（５）式のどちらを主体的に利用するかは、例えば、水素貯蔵率と、水素放出後の生成物に再び水素を吸蔵させる反応のサイクル特性（つまり、上記（４）式と上記（５）式の右辺から左辺への反応の容易さ）等とを考慮して、決定することができる。また、水素化リチウムとマグネシウムアミドのいずれか一方を他方に対して過剰とすることにより、その他方の物質の反応確率を上げて、水素放出を促進させることができると考えられる。しかし、一方の物質が過度に多すぎると、全量に対する水素貯蔵率を低下させてしまう問題が生ずる。 Which of these formulas (4) and (5) is mainly used depends on, for example, the hydrogen storage rate and the cycle characteristics of the reaction in which hydrogen is again stored in the product after hydrogen release (that is, the above-described formula). This can be determined in consideration of the equation (4) and the ease of reaction from the right side to the left side of the above equation (5). Moreover, it is thought that hydrogen release can be promoted by increasing the reaction probability of the other substance by making one of lithium hydride and magnesium amide excessive with respect to the other. However, if one of the substances is too much, there is a problem that the hydrogen storage rate with respect to the total amount is lowered.
したがって、このような水素貯蔵率や反応物質の利用率、水素吸放出反応のサイクル特性等を考慮して、水素化リチウムとマグネシウムアミドの各量を定めることが好ましい。具体的には、１モルのマグネシウムアミドに対する水素化リチウムの混合比を２モル以上５モル以下とすることが好ましく、さらに主に上記（５）式が進行するように、２．５モル以上３．５モル以下とすることで、水素貯蔵率をそれ以外の範囲よりも高く維持することができる。 Therefore, it is preferable to determine the respective amounts of lithium hydride and magnesium amide in consideration of such hydrogen storage rate, utilization rate of reactants, cycle characteristics of hydrogen absorption / release reaction, and the like. Specifically, the mixing ratio of lithium hydride to 1 mol of magnesium amide is preferably 2 mol or more and 5 mol or less, and more preferably 2.5 mol or more and 3 mol so that the above formula (5) proceeds mainly. By setting it to 0.5 mol or less, the hydrogen storage rate can be maintained higher than the other ranges.
別の好ましい組み合わせとしては、水素化マグネシウムとリチウムアミドの組み合わせが挙げられる。水素化マグネシウムとリチウムアミドとの反応は、下記（７）式および下記（８）式で示される。
ＭｇＨ２＋２ＬｉＮＨ２⇔Ｌｉ２ＮＨ＋ＭｇＮＨ＋２Ｈ２ …（７）
３ＭｇＨ２＋４ＬｉＮＨ２⇔Ｍｇ３Ｎ２＋２Ｌｉ２ＮＨ＋６Ｈ２ …（８）
Another preferred combination is a combination of magnesium hydride and lithium amide. The reaction between magnesium hydride and lithium amide is represented by the following formula (7) and the following formula (8).
MgH 2 + 2LiNH 2 ⇔Li 2 NH + MgNH + 2H 2 (7)
3MgH 2 + 4LiNH 2 ⇔Mg 3 N 2 + 2Li 2 NH + 6H 2 (8)
上記（７）式および（８）式を考察すると、上記（７）式では、１モルのリチウムアミドに対して０．５モルの水素化マグネシウムが化学等量であり、理論水素貯蔵率は５．４８質量％となる。一方、上記（８）式では、１モルのリチウムアミドに対して０．７５モルの水素化リチウムが化学等量であり、理論水素貯蔵率は７．０８質量％となる。したがって、水素化マグネシウムとリチウムアミドの組成比が変化することで支配的に起こる反応が変わり、また水素貯蔵率も変わってくることになる。 Considering the above formulas (7) and (8), in the above formula (7), 0.5 mol of magnesium hydride is equivalent to 1 mol of lithium amide, and the theoretical hydrogen storage rate is 5 48 mass%. On the other hand, in the above formula (8), 0.75 mol of lithium hydride is a chemical equivalent with respect to 1 mol of lithium amide, and the theoretical hydrogen storage rate is 7.08 mass%. Therefore, the reaction that occurs predominantly changes as the composition ratio of magnesium hydride and lithium amide changes, and the hydrogen storage rate also changes.
つまり、水素化マグネシウムとリチウムアミドの組み合わせの場合にも、前述した水素化リチウムとマグネシウムアミドの組み合わせの場合と同様に、水素貯蔵率や反応物質の利用率、水素吸放出反応のサイクル特性等を考慮して、水素化マグネシウムとリチウムアミドの各量を定めることが好ましい。具体的には、水素化マグネシウムを過剰とすることが好ましく、１モルのリチウムアミドに対する水素化マグネシウムの混合比を０．５モル以上３モル以下とすることが好ましい。さらに、さらに主に上記（８）式が進行するように、０．５モル以上１モル以下とすることで、水素貯蔵率をそれ以外の範囲よりも高く維持することができる。 In other words, in the case of the combination of magnesium hydride and lithium amide, as in the case of the combination of lithium hydride and magnesium amide described above, the hydrogen storage rate, the utilization rate of the reactants, the cycle characteristics of the hydrogen absorption / release reaction, etc. In consideration, it is preferable to determine the amounts of magnesium hydride and lithium amide. Specifically, the magnesium hydride is preferably excessive, and the mixing ratio of magnesium hydride to 1 mol of lithium amide is preferably 0.5 mol or more and 3 mol or less. Furthermore, the hydrogen storage rate can be maintained higher than the other ranges by setting the amount to 0.5 mol or more and 1 mol or less so that the formula (8) proceeds mainly.
ナノ粒子触媒の担持量は、金属水素化物と金属アミド化合物との混合物または複合化物の合計量の０．１質量％以上２０質量％以下とすることが好ましい。触媒添加率が０．１質量％未満では触媒としての効果が実質的に得られず、２０質量％超では水素吸放出反応が逆に阻害され、また全量に対する水素放出率が低下する。 The supported amount of the nanoparticle catalyst is preferably 0.1% by mass or more and 20% by mass or less of the total amount of the mixture or composite of the metal hydride and the metal amide compound. If the catalyst addition rate is less than 0.1% by mass, the effect as a catalyst is not substantially obtained, and if it exceeds 20% by mass, the hydrogen absorption / release reaction is adversely inhibited, and the hydrogen release rate with respect to the total amount decreases.
上述した第１の材料系に属する水素貯蔵材料の製造方法としては、以下に示す４方法のいずれかを用いることができる。第１の製造方法は、金属水素化物と金属アミド化合物に、ナノ粒子触媒を添加して、不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下（以下「不活性ガス雰囲気下等」という）において機械的粉砕処理により混合、微細化する方法である。 As a method for producing the hydrogen storage material belonging to the first material system described above, any of the following four methods can be used. In the first production method, a nanoparticle catalyst is added to a metal hydride and a metal amide compound, and an inert gas atmosphere, a hydrogen gas atmosphere, or a mixed gas atmosphere of an inert gas and a hydrogen gas (hereinafter, “ In an inert gas atmosphere etc.)) and mixing and refining by mechanical pulverization.
第２の製造方法は、金属水素化物と金属アミド化合物を不活性ガス雰囲気下等において機械的粉砕処理により混合、微細化し、こうして得られた被処理物にナノ粒子触媒を添加して、被処理物にナノ粒子触媒を担持させる方法である。 In the second production method, a metal hydride and a metal amide compound are mixed and refined by mechanical pulverization in an inert gas atmosphere or the like, and a nanoparticle catalyst is added to the object to be processed thus obtained. This is a method of supporting a nanoparticle catalyst on a product.
第３の製造方法は、金属水素化物または金属アミド化合物のいずれか一方にナノ粒子触媒を添加して、不活性ガス雰囲気下等において機械的粉砕処理により混合、微細化し、次に得られた被処理物と他方とを、不活性ガス雰囲気下等において混合粉砕する方法である。 In the third production method, a nanoparticle catalyst is added to either a metal hydride or a metal amide compound, mixed and refined by mechanical pulverization in an inert gas atmosphere or the like, and then the obtained coating is obtained. In this method, the processed product and the other are mixed and pulverized in an inert gas atmosphere or the like.
第４の製造方法は、金属水素化物と金属アミド化合物それぞれにナノ粒子触媒を添加して、金属水素化物と金属アミド化合物ごとに、不活性ガス雰囲気下等において機械的粉砕処理により混合、微細化し、こうして得られた被処理物どうしを、不活性ガス雰囲気下等において混合粉砕する方法である。後段の混合粉砕処理は、実質的に粉砕が起こらない条件での混合処理であってもよい。 In the fourth production method, a nanoparticle catalyst is added to each of the metal hydride and the metal amide compound, and the metal hydride and the metal amide compound are mixed and refined by mechanical pulverization in an inert gas atmosphere or the like. In this method, the objects to be processed thus obtained are mixed and ground in an inert gas atmosphere or the like. The subsequent mixing and pulverizing process may be a mixing process under conditions where pulverization does not occur substantially.
本発明の第２の材料系は、金属イミド化合物とナノ粒子触媒を含み、かつ、水素化された水素貯蔵材料である。ここで、本明細書において「物質の水素化」とは、その物質と水素とを反応させることによって、その物質が水素を取り込んだ状態に変化することをいうものとする。 The second material system of the present invention is a hydrogenated hydrogen storage material containing a metal imide compound and a nanoparticle catalyst. Here, in this specification, “hydrogenation of a substance” means that the substance is changed to a state in which hydrogen is incorporated by reacting the substance with hydrogen.
この第２の材料系に属する水素貯蔵材料としては、水素化したリチウムイミドが挙げられる。前記水素化の定義によれば、水素化したリチウムイミドは、リチウムイミドを水素と反応させることにより得られ、その構造は明らかでないが、リチウムアミドやアンモニアに変化することなく、水素と反応して水素を何らかの形で取り込んでおり、後に所定温度に加熱すると取り込まれた水素が放出されて元のリチウムイミドに戻る材料をいう。 Examples of the hydrogen storage material belonging to the second material system include hydrogenated lithium imide. According to the definition of hydrogenation, hydrogenated lithium imide is obtained by reacting lithium imide with hydrogen, and its structure is not clear, but it reacts with hydrogen without changing to lithium amide or ammonia. This refers to a material that has taken in hydrogen in some form and returns to the original lithium imide when it is heated to a predetermined temperature later.
リチウムイミドの水素化は、リチウムイミドを所定圧力、所定温度の水素ガス雰囲気下で所定時間保持することにより行うことができる。ナノ粒子触媒の担持量は、第１の材料系の場合と同様の理由により、金属イミド化合物の全量の０．１質量％以上２０質量％以下とすることが好ましい。 Hydrogenation of lithium imide can be performed by holding lithium imide in a hydrogen gas atmosphere at a predetermined pressure and a predetermined temperature for a predetermined time. The supported amount of the nanoparticle catalyst is preferably 0.1% by mass or more and 20% by mass or less of the total amount of the metal imide compound for the same reason as in the first material system.
リチウムイミドは、窒化リチウムを水素と反応させ、またはリチウムアミドを熱分解することにより合成することが好ましい。これは次のような理由による。すなわち、リチウムイミドは水素化リチウムとリチウムアミドとを混合して反応させることにより合成することもできるが、この場合には固相反応となるために、ミクロな状態で水素化リチウムとリチウムアミドを均質に接触させるために大きな機械的エネルギーが必要になるという問題がある。これに対して、リチウムイミドを熱分解等により合成すれば、その過程でリチウムイミドの比表面積が大きくなり、水素化が進行しやすくなるというメリットがある。 Lithium imide is preferably synthesized by reacting lithium nitride with hydrogen or thermally decomposing lithium amide. This is due to the following reason. In other words, lithium imide can be synthesized by mixing lithium hydride and lithium amide and reacting them, but in this case, since it becomes a solid-phase reaction, lithium hydride and lithium amide are in a microscopic state. There is a problem that a large amount of mechanical energy is required for homogeneous contact. On the other hand, when lithium imide is synthesized by thermal decomposition or the like, there is an advantage that the specific surface area of lithium imide increases in the process and hydrogenation easily proceeds.
また、第２の材料系には、金属イミド化合物と金属窒化物とナノ粒子触媒を含み、かつ、水素化された水素貯蔵材料が含まれる。具体例としては、リチウムイミドと窒化マグネシウムとナノ粒子触媒を含み、これを水素化したものが挙げられる。この材料の場合にも、ナノ粒子触媒の担持量は、リチウムイミドおよび窒化マグネシウムの合計量の０．１質量％以上２０質量％以下とすることが好ましい。 The second material system also includes a hydrogenated hydrogen storage material that includes a metal imide compound, a metal nitride, and a nanoparticle catalyst. Specific examples include lithium imide, magnesium nitride, and a nanoparticle catalyst, which are hydrogenated. Also in the case of this material, the supported amount of the nanoparticle catalyst is preferably 0.1% by mass or more and 20% by mass or less of the total amount of lithium imide and magnesium nitride.
上述した各種の水素貯蔵材料に含まれるナノ粒子触媒としては、Ｂ，Ｃ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｐｔ，Ｐｄ，Ｒｈ，Ｌｉ，Ｎａ，Ｍｇ，Ｋ，Ｉｒ，Ｎｄ，Ｎｂ，Ｌａ，Ｃａ，Ｖ，Ｔｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ａｌ，Ｓｉ，Ｒｕ，Ｍｏ，Ｗ，Ｔａ，Ｚｒ，ＨｆおよびＡｇから選ばれた１種または２種以上の金属、またはその化合物またはその合金、あるいは水素貯蔵合金が好適に用いられる。ナノ粒子触媒の形態としては、ナノ金属粒子、ナノ金属酸化物粒子、ナノ金属塩化物が好適に用いられる。ナノ粒子触媒のさらに好ましい例としては、ＴｉＯ２（アナターゼ型）ナノ粒子、Ｔｉナノ粒子が挙げられる。 Nanoparticle catalysts contained in the various hydrogen storage materials described above include B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, One or more metals selected from Ca, V, Ti, Cr, Cu, Zn, Al, Si, Ru, Mo, W, Ta, Zr, Hf, and Ag, or a compound or alloy thereof, or A hydrogen storage alloy is preferably used. As the form of the nanoparticle catalyst, nanometal particles, nanometal oxide particles, and nanometal chloride are preferably used. More preferable examples of the nanoparticle catalyst include TiO 2 (anatase type) nanoparticles and Ti nanoparticles.
このような第２の材料系に属する水素貯蔵材料の製造方法としては、以下の４方法が好適に用いられる。第１の製造方法は、金属イミド化合物にナノ粒子触媒を添加して、不活性ガス雰囲気下等において所定の機械的粉砕処理により混合、微細化し、その後に水素化する方法である。 As a method for producing such a hydrogen storage material belonging to the second material system, the following four methods are preferably used. The first production method is a method in which a nanoparticle catalyst is added to a metal imide compound, mixed and refined by a predetermined mechanical pulverization treatment in an inert gas atmosphere or the like, and then hydrogenated.
第２の製造方法は、金属窒化物と金属イミド化合物を不活性ガス雰囲気下等において所定の機械的粉砕処理により混合、微細化し、こうして得られた被処理物にナノ粒子触媒を添加して、被処理物にナノ粒子触媒を担持させ、その後に水素化する方法である。 In the second production method, a metal nitride and a metal imide compound are mixed and refined by a predetermined mechanical pulverization process in an inert gas atmosphere or the like, and a nanoparticle catalyst is added to the object to be processed thus obtained. In this method, a nanoparticle catalyst is supported on an object to be treated and then hydrogenated.
第３の製造方法は、金属窒化物または金属イミド化合物のいずれか一方にナノ粒子触媒を添加して、不活性ガス雰囲気下等において機械的粉砕処理により混合、微細化し、こうして得られた被処理物と他方とを不活性ガス雰囲気下等において混合粉砕し、その後に水素化する方法である。 In the third production method, the nanoparticle catalyst is added to one of the metal nitride and the metal imide compound, mixed and refined by mechanical pulverization in an inert gas atmosphere or the like, and the treatment object thus obtained is obtained. In this method, the product and the other are mixed and pulverized in an inert gas atmosphere or the like, and then hydrogenated.
第４の製造方法は、金属窒化物と金属イミド化合物それぞれにナノ粒子触媒を添加して、金属窒化物と金属イミド化合物ごとに不活性ガス雰囲気下等において機械的粉砕処理により混合、微細化し、こうして得られた被処理物どうしを不活性ガス雰囲気下等において混合粉砕し、その後に水素化する方法である。後段の混合粉砕処理は、実質的に粉砕が起こらない条件での混合処理であってもよい。 In the fourth production method, a nanoparticle catalyst is added to each of the metal nitride and the metal imide compound, and the metal nitride and the metal imide compound are mixed and refined by mechanical pulverization in an inert gas atmosphere or the like. In this method, the workpieces thus obtained are mixed and pulverized in an inert gas atmosphere or the like and then hydrogenated. The subsequent mixing and pulverizing process may be a mixing process under conditions where pulverization does not occur substantially.
上記各材料系に属する水素貯蔵材料の機械的粉砕処理は、原料粉末を、例えば、ボールミル装置、ローラーミル、内外筒回転型ミル、アトライター、インナーピース型ミル、気流粉砕型ミル等の公知の種々の粉砕手段を用いて行うことができる。このような機械的粉砕処理では、粉砕助剤として、無機質担体、合成品担体、植物担体や有機溶剤などを添加することは、効率よく原料粉末を微細化する上で有効である。 The mechanical pulverization treatment of the hydrogen storage material belonging to each of the above-mentioned material systems is performed by using a known raw material powder such as a ball mill apparatus, a roller mill, an inner / outer cylinder rotating mill, an attritor, an inner piece mill, an airflow milling mill, etc. Various pulverization means can be used. In such a mechanical pulverization treatment, adding an inorganic carrier, a synthetic carrier, a plant carrier, an organic solvent, or the like as a pulverization aid is effective in efficiently refining the raw material powder.
（１）ＬｉＨ＋ＬｉＮＨ２系試料（実施例１，２、比較例１，２）の作製
表１に示すように、水素化リチウムとリチウムアミド（いずれもアルドリッチ社製、純度９５％）と各種触媒とを、モル比が１：１：０．０２でその合計量が１．３ｇとなるように、高純度アルゴングローブボックス中で秤量し、高クロム鋼製のバルブ付ミル容器（２５０ｍｌ）に投入した。続いて、このミル容器内を真空排気した後、高純度アルゴンガスを１ＭＰａ導入し、遊星型ボールミル装置（Ｆｒｉｔｓｃｈ社製、Ｐ−５）を用いて、室温、２５０ｒｐｍで１２０分ミリング処理した。ミル容器内を真空排気してアルゴンガスを充填した後、高純度アルゴングローブボックス中でミル容器を開き、試料を取り出した。
(1) Preparation of LiH + LiNH 2 System Samples (Examples 1 and 2, Comparative Examples 1 and 2) As shown in Table 1, lithium hydride and lithium amide (all manufactured by Aldrich, purity 95%), various catalysts, Was weighed in a high-purity argon glove box so that the molar ratio was 1: 1: 0.02 and the total amount was 1.3 g, and charged into a high-chromium steel valve vessel (250 ml). . Subsequently, after the inside of the mill container was evacuated, 1 MPa of high-purity argon gas was introduced, and milling was performed at room temperature and 250 rpm for 120 minutes using a planetary ball mill apparatus (P-5, manufactured by Fritsch). After the inside of the mill container was evacuated and filled with argon gas, the mill container was opened in a high purity argon glove box, and a sample was taken out.
なお、ＴｉＯ２ナノ粒子はミレニアムケミカルズ社製の純度が８２．８％でＢＥＴ比表面積が１２９．８ｍ２／ｇ、ＴｉＯ２マイクロ粒子はアルドリッチ社製で純度が９９．９％でＢＥＴ比表面積が１８ｍ２／ｇ、Ｔｉナノ粒子は平均粒径が１ｎｍ、Ｔｉマイクロ粒子はレアメタル社製の純度が９９．９％で粒子径が１０〜１００μｍ、である。 The TiO 2 nanoparticles have a purity of 82.8% and a BET specific surface area of 129.8 m 2 / g manufactured by Millennium Chemicals, and the TiO 2 microparticles have a purity of 99.9% and a BET specific surface area of 99.9%. 18 m 2 / g, Ti nanoparticles have an average particle diameter of 1 nm, and Ti microparticles have a purity of 99.9% and a particle diameter of 10 to 100 μm manufactured by Rare Metal.
（２）リチウムイミド系試料（実施例３，４、比較例３，４）の作製
表２に示すように最終的にリチウムイミドと各種触媒とがモル比で１：０．０２となるように、原料たるリチウムアミド（アルドリッチ社製、純度９５％）と各種触媒とを、モル比が１：０．０１でその合計量が１．３ｇとなるように高純度アルゴングローブボックス中で秤量し、高クロム鋼製のバルブ付ミル容器（２５０ｍｌ）に投入した。続いて、このミル容器内を真空排気した後、高純度アルゴンガスを１ＭＰａ導入し、遊星型ボールミル装置を用いて、室温、２５０ｒｐｍで１２０分ミリング処理を行った。続いて、ミル容器内を真空排気してアルゴンガスを充填した後、高純度アルゴングローブボックス中でミル容器を開き、試料を取り出してステンレス製の反応容器（５０ｍｌ）に移した。この反応容器内を真空排気した後、３５０℃で６時間熱処理することでリチウムアミドを熱分解し、各種触媒を担持したリチウムイミドを合成した。さらに得られたリチウムイミドを水素ガス中、３ＭＰａ、１８０℃で１２時間処理し、水素化した。
(2) Preparation of Lithiumimide Samples (Examples 3 and 4, Comparative Examples 3 and 4) As shown in Table 2, finally, the lithium imide and various catalysts were in a molar ratio of 1: 0.02. The raw material lithium amide (manufactured by Aldrich, purity 95%) and various catalysts were weighed in a high-purity argon glove box so that the molar ratio was 1: 0.01 and the total amount was 1.3 g. It was put into a mill vessel with a valve (250 ml) made of high chromium steel. Subsequently, after the inside of the mill container was evacuated, 1 MPa of high-purity argon gas was introduced, and a milling process was performed at room temperature and 250 rpm for 120 minutes using a planetary ball mill apparatus. Subsequently, after the inside of the mill container was evacuated and filled with argon gas, the mill container was opened in a high-purity argon glove box, and the sample was taken out and transferred to a stainless steel reaction container (50 ml). After evacuating the inside of the reaction vessel, the lithium amide was thermally decomposed by heat treatment at 350 ° C. for 6 hours to synthesize lithium imide carrying various catalysts. Further, the obtained lithium imide was treated in hydrogen gas at 3 MPa and 180 ° C. for 12 hours to be hydrogenated.
（３）ＬｉＨ＋Ｍｇ（ＮＨ２）２系試料（実施例５，６、比較例５，６）の作製
最初に水素化マグネシウム（アヅマックス社製、純度９５％）をアンモニアと反応させてマグネシウムアミドを合成した。次に、表３に示すように、水素化リチウム（アルドリッチ社製、純度９５％）と合成したマグネシウムアミドと各種触媒とを、モル比が８：３：０．１１でその合計量が１．３ｇとなるように高純度アルゴングローブボックス中で秤量し、高クロム鋼製のバルブ付ミル容器（２５０ｍｌ）に投入した。続いて、このミル容器内を真空排気した後、高純度アルゴンガスを１ＭＰａ導入し、遊星型ボールミル装置を用いて、室温、２５０ｒｐｍで所定時間ミリング処理した。ミル容器内を真空排気してアルゴンガスを充填した後、高純度アルゴングローブボックス中でミル容器を開き、試料を取り出した。
(3) Production of LiH + Mg (NH 2 ) 2 System Samples (Examples 5 and 6, Comparative Examples 5 and 6) First, magnesium hydride (manufactured by Amax Co., purity 95%) was reacted with ammonia to synthesize magnesium amide. did. Next, as shown in Table 3, lithium hydride (manufactured by Aldrich, purity 95%), synthesized magnesium amide, and various catalysts were in a molar ratio of 8: 3: 0.11 and the total amount was 1. It was weighed in a high purity argon glove box so as to be 3 g, and put into a mill vessel with a valve (250 ml) made of high chromium steel. Subsequently, after the inside of the mill container was evacuated, 1 MPa of high-purity argon gas was introduced, and milling was performed at room temperature and 250 rpm for a predetermined time using a planetary ball mill apparatus. After the inside of the mill container was evacuated and filled with argon gas, the mill container was opened in a high purity argon glove box, and a sample was taken out.
（４）ＬｉＮＨ２＋ＭｇＨ２系試料（実施例７，８、比較例７，８）の作製
表４に示すように、リチウムアミドと水素化マグネシウムと各種触媒を、モル比が４：３：０．０７でその合計量が１．３ｇとなるように高純度アルゴングローブボックス中で秤量し、高純度アルゴンガスを１ＭＰａ導入し、遊星型ボールミル装置を用いて、室温、２５０ｒｐｍで所定時間ミリング処理した。ミル容器内を真空排気してアルゴンガスを充填した後、高純度アルゴングローブボックス中でミル容器を開き、試料を取り出した。
(4) Production of LiNH 2 + MgH 2 Samples (Examples 7 and 8, Comparative Examples 7 and 8) As shown in Table 4, the molar ratio of lithium amide, magnesium hydride, and various catalysts was 4: 3: 0. 0.07, and weighed in a high purity argon glove box so that the total amount becomes 1.3 g, introduced 1 MPa of high purity argon gas, and milled for a predetermined time at 250 rpm at room temperature using a planetary ball mill device. . After the inside of the mill container was evacuated and filled with argon gas, the mill container was opened in a high purity argon glove box, and a sample was taken out.
（５）Ｌｉ２ＮＨ＋Ｍｇ３Ｎ２系試料（実施例９，１０、比較例９，１０）の作製
表５に示すように、上記（３）に記載の方法で合成したリチウムイミドと窒化マグネシウム（アルドリッチ社製、純度９５％）に各種触媒とを、モル比が４：１：０．０５でその合計量が１．３ｇとなるように高純度アルゴングローブボックス中で秤量し、高クロム鋼製のバルブ付ミル容器（２５０ｍｌ）に投入した。続いて、このミル容器内を真空排気した後、高純度アルゴンガスを１ＭＰａ導入し、遊星型ボールミル装置を用いて、室温、２５０ｒｐｍで所定時間ミリング処理した。ミル容器内を真空排気してアルゴンガスを充填した後、高純度アルゴングローブボックス中でミル容器を開き、試料を取り出した。さらに得られた被処理物を水素ガス中、３ＭＰａ、２２０℃で１２時間処理し、水素化した。
(5) Production of Li 2 NH + Mg 3 N 2 System Samples (Examples 9 and 10, Comparative Examples 9 and 10) As shown in Table 5, lithium imide and magnesium nitride synthesized by the method described in (3) above ( Aldrich (purity 95%) and various catalysts were weighed in a high-purity argon glove box so that the total amount was 1.3 g with a molar ratio of 4: 1: 0.05 and made of high chromium steel. In a mill vessel with a valve (250 ml). Subsequently, after the inside of the mill container was evacuated, 1 MPa of high-purity argon gas was introduced, and milling was performed at room temperature and 250 rpm for a predetermined time using a planetary ball mill apparatus. After the inside of the mill container was evacuated and filled with argon gas, the mill container was opened in a high purity argon glove box, and a sample was taken out. Further, the obtained object to be treated was treated with hydrogen in hydrogen gas at 3 MPa and 220 ° C. for 12 hours to be hydrogenated.
（６）試料評価
ＢＥＴ比表面積の測定は、窒素ガスによる多点式ＢＥＴ測定（Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製、ＡＳＡＰ２４００）により行った。また、高純度アルゴングローブボックス内に設置されたＴＧ−ＭＡＳＳ装置（熱重量・質量分析装置）を用い、昇温速度を５℃／分として昇温して水素放出スペクトルを測定し、そのピーク温度を水素放出温度とした。
(6) Sample evaluation The BET specific surface area was measured by multipoint BET measurement using nitrogen gas (ASAP2400, manufactured by Micromeritics). In addition, using a TG-MASS device (thermogravimetric / mass spectrometer) installed in a high purity argon glove box, the temperature was raised at a rate of temperature rise of 5 ° C./minute, and the hydrogen release spectrum was measured. Was the hydrogen release temperature.
（７）試験結果
図１に実施例１および比較例１の水素放出スペクトルを示すグラフを示し、図２に実施例２および比較例２の水素放出スペクトルを示すグラフを示す。また、実施例１，２および比較例１，２の水素放出温度を表１に併記する。図１および図２ならびに表１から、ナノ粒子触媒を用いることによって、水素放出反応が起こる温度範囲が狭くなって、水素放出温度が低温側にシフトしていることがわかる。これにより、例えば２５０℃で実施例１と比較例１とを比べると、２５０℃までに放出される水素の全量は、実施例１の方が比較例１よりも多くなる。実施例２と比較例２についても同様のことが言える。
(7) Test Results FIG. 1 shows a graph showing the hydrogen release spectra of Example 1 and Comparative Example 1, and FIG. 2 shows a graph showing the hydrogen release spectra of Example 2 and Comparative Example 2. The hydrogen release temperatures of Examples 1 and 2 and Comparative Examples 1 and 2 are also shown in Table 1. From FIG. 1 and FIG. 2 and Table 1, it can be seen that by using the nanoparticle catalyst, the temperature range where the hydrogen releasing reaction occurs is narrowed, and the hydrogen releasing temperature is shifted to the low temperature side. Thereby, for example, when Example 1 and Comparative Example 1 are compared at 250 ° C., the total amount of hydrogen released up to 250 ° C. is larger in Example 1 than in Comparative Example 1. The same can be said for Example 2 and Comparative Example 2.
実施例３〜１０および比較例３〜１０の水素放出温度は表２〜表５に併記している。これらの表からも、ナノ粒子触媒を用いた場合に水素放出温度が低温側にシフトしていることが確認された。 The hydrogen release temperatures of Examples 3 to 10 and Comparative Examples 3 to 10 are shown in Tables 2 to 5. From these tables, it was confirmed that the hydrogen release temperature was shifted to the low temperature side when the nanoparticle catalyst was used.
本発明に係る水素貯蔵材料は、水素と酸素を燃料として発電する燃料電池の水素源として好適である。 The hydrogen storage material according to the present invention is suitable as a hydrogen source of a fuel cell that generates power using hydrogen and oxygen as fuel.
Claims (10)
前記触媒はＴｉＯ ２ ナノ粒子またはＴｉナノ粒子からなり、
前記金属水素化物と金属アミド化合物の金属種が２種であって、金属種はリチウムおよびマグネシウムであることを特徴とする水素貯蔵材料。 A hydrogen storage material comprising a mixture or composite comprising a metal hydride, a metal amide compound, and a catalyst for enhancing hydrogen absorption / release capability,
The catalyst Ri TiO 2 nanoparticles or Ti nanoparticles Tona,
A hydrogen storage material, wherein the metal hydride and the metal amide compound have two metal species, and the metal species are lithium and magnesium .
前記金属水素化物と前記金属アミド化合物に、前記触媒を添加して、不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下において機械的粉砕処理により混合、微細化することを特徴とする水素貯蔵材料の製造方法。 A mixture or composite comprising a metal hydride, a metal amide compound, and a catalyst that enhances hydrogen absorption / release capability, the catalyst comprising TiO 2 nanoparticles or Ti nanoparticles, and the metal hydride and the metal of the metal amide compound A method for producing a hydrogen storage material, wherein the species is two species and the metal species are lithium and magnesium,
To the metal hydride and the metal amide compound with the addition of the catalyst, mixing by mechanical pulverization treatment in a mixed gas atmosphere of an inert gas atmosphere or hydrogen gas atmosphere or an inert gas and hydrogen gas, fine A method for producing a hydrogen storage material, characterized by comprising:
前記金属水素化物と前記金属アミド化合物を不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下において機械的粉砕処理により混合、微細化する第１工程と、
前記第１工程により得られた被処理物に、前記触媒を添加して、前記被処理物に前記触媒を担持させる第２工程と、
を有することを特徴とする水素貯蔵材料の製造方法。 A mixture or composite comprising a metal hydride, a metal amide compound, and a catalyst that enhances hydrogen absorption / release capability, the catalyst comprising TiO 2 nanoparticles or Ti nanoparticles, and the metal hydride and the metal of the metal amide compound A method for producing a hydrogen storage material, wherein the species is two species and the metal species are lithium and magnesium,
Mixed by mechanical pulverization treatment under a mixed gas atmosphere of said metal hydride with said metal amide compound an inert gas atmosphere or hydrogen gas atmosphere or an inert gas and hydrogen gas, a first step of refining,
A second step of adding the catalyst to the object to be processed obtained in the first step and loading the catalyst on the object to be processed;
A method for producing a hydrogen storage material, comprising:
前記金属水素化物または前記金属アミド化合物のいずれか一方に、前記触媒を添加して、不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下において、機械的粉砕処理により混合、微細化する第１工程と、
前記第１工程により得られた被処理物と他方とを、不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下において、混合粉砕する工程と、
を有することを特徴とする水素貯蔵材料の製造方法。 A mixture or composite comprising a metal hydride, a metal amide compound, and a catalyst that enhances hydrogen absorption / release capability, the catalyst comprising TiO 2 nanoparticles or Ti nanoparticles, and the metal hydride and the metal of the metal amide compound A method for producing a hydrogen storage material, wherein the species is two species and the metal species are lithium and magnesium,
Any one of the metal hydride or the metal amide compound with the addition of the catalyst, a mixed gas atmosphere of an inert gas atmosphere or hydrogen gas atmosphere or an inert gas and hydrogen gas, mechanical pulverization A first step of mixing and refining by processing;
Mixing and pulverizing the object to be processed and the other obtained in the first step under an inert gas atmosphere or a hydrogen gas atmosphere or a mixed gas atmosphere of an inert gas and hydrogen gas;
A method for producing a hydrogen storage material, comprising:
前記金属水素化物と前記金属アミド化合物それぞれに、前記触媒を添加して、前記金属水素化物と金属アミド化合物ごとに、不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下において、機械的粉砕処理により混合、微細化する第１工程と、
前記第１工程により得られた被処理物どうしを、不活性ガス雰囲気下もしくは水素ガス雰囲気下または不活性ガスと水素ガスとの混合ガス雰囲気下において、混合粉砕する第２工程と、
を有することを特徴とする水素貯蔵材料の製造方法。 A mixture or composite comprising a metal hydride, a metal amide compound, and a catalyst that enhances hydrogen absorption / release capability, the catalyst comprising TiO 2 nanoparticles or Ti nanoparticles, and the metal hydride and the metal of the metal amide compound A method for producing a hydrogen storage material, wherein the species is two species and the metal species are lithium and magnesium,
Each said metal hydride with said metal amide compound with the addition of the catalyst, mixing with the per metal hydride and a metal amide compound, under an inert gas atmosphere or under a hydrogen gas atmosphere or an inert gas and hydrogen gas A first step of mixing and refining by a mechanical pulverization process in a gas atmosphere;
A second step of mixing and grinding the objects to be processed obtained in the first step under an inert gas atmosphere or a hydrogen gas atmosphere or a mixed gas atmosphere of an inert gas and hydrogen gas;
A method for producing a hydrogen storage material, comprising:
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