JP2009195903A - 可逆的な水素吸蔵用の不安定化触媒化ホウ水素化物 - Google Patents
可逆的な水素吸蔵用の不安定化触媒化ホウ水素化物 Download PDFInfo
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Abstract
【解決手段】Mはアルカリ金属又はアルカリ土類金属であり、化学式M(BH4)Xの第1の材料を用意し、M(AlH4)X、M(AlH4)XとMClXの混合物、MClXとAlの混合物、MClXとAlH3の混合物、MHXとAlの混合物、Al、及びAlH3から選択される第2の材料を用意する、ステップを含む水素吸蔵材料の形成方法。第1の材料よりも低い水素放出温度を有し、第2の材料よりも高い水素質量密度を有する第3の材料を形成する時間、第1と第2の材料を高温の高水素ガス圧力下で組み合わせる。
【選択図】図1
Description
上述の手順を用いて、LiBH4を0.2モルのマグネシウムと混合し、部分的な置換物を得た。図6〜8に示すように、市販の純粋なLiBH4が325℃で水素を放出するのに対して、不安定化した材料LiBH4+0.2Mgは60℃で水素を放出する。室温では、2つのラマン活性内部BH4 -1振動v4及びv’4がそれぞれ1253cm-1と1287cm-1で発生し、2つの倍音振動2v4及び2v4’がそれぞれ2240cm-1と2274cm-1で発生していることが、図7のスペクトル2にみられる。しかしながら、不安定化したLiBH4+0.2Mgを添加すると、v4、v’4、及び2v4のピークは、スペクトルから消える。スペクトル1に示すように、2v4’のピークは小さくなり2300cm-1にシフトし、部分的なLi+の置換によって、B−H結合強度が減少することを示している。結合が弱まることによって、水素脱離温度は低くなる。図8にこれまで示したように、部分的に置換したLiBH4材料は、再水素化の多重サイクルを達成することができる。
LiBH4を、0.2モルのTiCl3を加えた0.3MgCl2と組み合わせて、上述のプロセスに通した。図9に示すように、部分的に置換した生成物は、市販のLiBH4と比較して、水素の脱離放出の温度特性と、500℃以下の温度で放出する水素の割合を改良した。
LiBH4を、0.007TiCl3を加えた0.5MgH2と混合し、及び上述のステップにしたがったプロセス処理を行った。図12に、得られた生成物の温度による水素脱離データを示す。
80質量%のLiBH4を0.2モルのAlと組み合わせて、上述の手順で処理した。図14と図15に、水素脱離と再水素化のそれぞれのデータを示した。
LiBH4を0.5LiAlH4と組み合わせて、上述の手順に通した。図16と図17にみられるように、部分的に置換したLiBH4の水素脱離特性と再水素化特性をそれぞれ示した。
等モルのLiBH4とNaAlH4の混合物を、上述の手順にしたがって準備した。図18に、改良した水素脱離特性を示した。
Claims (13)
- 化学式M(BH4)X(式中、Mはアルカリ金属又はアルカリ土類金属で、1≦X≦2)である第1の材料を用意し、
M(AlH4)X(1≦X≦4)、M(AlH4)X(1≦X≦4)とMClX(1≦X≦4)の混合物、MClX(1≦X≦4)とAlの混合物、MClX(1≦X≦4)とAlH3の混合物、MHX(1≦X≦2)とAl又はAlH3の混合物、Al、及びAlH3から選択される第2の材料を用意し、
該第1の材料よりも低い水素放出温度を有する第3の材料を形成する時間、該第1と該第2の材料を高温の高水素ガス圧力下で組み合わせる、
ステップを含む水素吸蔵材料の形成方法。 - 該第3の材料が該第2の材料よりも高い水素質量密度を有する、請求項1に記載の方法。
- 該第1と該第2の材料を組み合わせるステップの前に、該第1と該第2の材料をボールミル粉砕するステップを含む、請求項1に記載の方法。
- 該第1と該第2の材料を約50〜100ナノメートルの粒子サイズに粉砕する、請求項3に記載の方法。
- 該第3の材料が可逆的に水素を吸蔵する、請求項1に記載の方法。
- 該第3の材料が再水素化されるとき、該第3の材料がその後に可逆的に少なくとも約6質量%の水素を放出する、請求項1に記載の方法。
- 該第1の材料が、水素化ホウ素リチウム、水素化ホウ素ナトリウム、水素化ホウ素カリウム、又はそれらの組み合わせからなる群から選択される、請求項1に記載の方法。
- 該アルカリ土類金属が、マグネシウム、カルシウム、ストロンチウム、バリウム、アルミニウム、及びそれらの組み合わせからなる群から選択される、請求項1に記載の方法。
- MClXが、MgCl2、CaCl2、SrCl2、BaCl3、ZrCl4、TiCl3、及びそれらの組み合わせからなる群から選択される、請求項1に記載の方法。
- MHXが、MgH2、CaH2、TiH2、ZrH2、及びそれらの組み合わせからなる群から選択される、請求項1に記載の方法。
- M(AlH4)Xが、LiAlH4、NaAlH4、Mg(AlH4)2、及びCa(AlH4)2からなる群から選択される、請求項1に記載の方法。
- 化学式M(BH4)X(式中、Mはアルカリ金属又はアルカリ土類金属で、1≦X≦2)である第1の材料を用意し、
M(AlH4)X(1≦X≦4)、M(AlH4)X(1≦X≦4)とMClX(1≦X≦4)の混合物、MClX(1≦X≦4)とAlの混合物、MClX(1≦X≦4)とAlH3の混合物、MHX(1≦X≦2)とAl又はAlH3の混合物、Al、及びAlH3から選択される第2の材料を用意し、
可逆的に水素を吸蔵する第3の材料を形成する時間、該第1と該第2の材料を高温の高水素ガス圧力下で組み合わせる、
ステップを含む水素吸蔵材料の形成方法。 - 化学式M(BH4)X(式中、Mはアルカリ金属又はアルカリ土類金属で、1≦X≦2)である第1の材料を用意し、
M(AlH4)X(1≦X≦4)、M(AlH4)X(1≦X≦4)とMClX(1≦X≦4)の混合物、MClX(1≦X≦4)とAlの混合物、MClX(1≦X≦4)とAlH3の混合物、MHX(1≦X≦2)とAl又はAlH3の混合物、Al、及びAlH3から選択される第2の材料を用意し、
該第1の材料よりも低い水素放出温度を有し該第2の材料よりも高い水素質量密度を有する第3の材料を形成する時間、該第1と該第2の材料を高温の高水素ガス圧力下で組み合わせる、
ステップを含む水素吸蔵材料の形成方法。
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JP2011005485A (ja) * | 2009-06-16 | 2011-01-13 | Toyota Motor Engineering & Manufacturing North America Inc | 可逆的な水素貯蔵のための不安定化及び触媒された水素化ホウ素 |
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US20110142754A1 (en) * | 2009-12-10 | 2011-06-16 | Jie-Ren Ku | One-off and adjustment method of hydrogen releasing from chemical hydride |
US20110143240A1 (en) * | 2009-12-10 | 2011-06-16 | Industrial Technology Research Institute | Hydrogen Generation System, Method for Generating Hydrogen Using Solid Hydrogen Fuel and Method for Providing Hydrogen for Fuel Cell Using the Same |
US9067784B2 (en) | 2012-06-06 | 2015-06-30 | Ford Global Technologies, Llc | Hydrogen storage material and method of using the same |
US20150307962A1 (en) * | 2014-04-23 | 2015-10-29 | Saint Louis University | Novel Hydrogen-Evolving Polymer-Capped Aluminum Nanoparticles, Composites, and Methods of Synthesis Using Lithium Aluminum Hydride |
DE102014006373A1 (de) * | 2014-05-05 | 2015-11-05 | Gkn Sinter Metals Engineering Gmbh | Wasserstoffspeicher mit kompensierter Volumenänderung |
Citations (7)
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JPS538393A (en) * | 1976-06-28 | 1978-01-25 | Raffinage Cie Francaise | Store*manufacture and application of bonded hydrogen |
JP2001519312A (ja) * | 1997-10-10 | 2001-10-23 | マクギル ユニバーシティ | 複合体アルカリ金属水素化物の製造方法 |
JP2004196634A (ja) * | 2002-12-20 | 2004-07-15 | Honda Motor Co Ltd | 水素貯蔵・放出システムに用いられる水素化物粉末 |
JP2005186058A (ja) * | 2003-12-03 | 2005-07-14 | Toyota Central Res & Dev Lab Inc | マグネシウム系水素吸蔵材料およびリチウム系水素吸蔵材料 |
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JP2007117989A (ja) * | 2005-09-27 | 2007-05-17 | Toyota Central Res & Dev Lab Inc | 水素貯蔵材料及びその製造方法 |
WO2009062850A1 (de) * | 2007-11-16 | 2009-05-22 | Gkss-Forschungszentrum Geesthacht Gmbh | Wasserstoff speichernde kompositmaterialien |
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DE19526434A1 (de) * | 1995-07-19 | 1997-01-23 | Studiengesellschaft Kohle Mbh | Verfahren zur reversilben Speicherung von Wasserstoff |
WO2004041717A1 (en) * | 2002-11-01 | 2004-05-21 | Westinghouse Savannah River Company, Llc | Complex hydrides for hydrogen storage |
EP1697258A4 (en) * | 2003-11-26 | 2010-03-10 | Cabot Corp | PARTICULATE ABSORBENT MATERIALS AND PROCESSES FOR PRODUCING THE SAME |
US20060194695A1 (en) * | 2004-08-27 | 2006-08-31 | Westinghouse Savannah River Co., Llc | Destabilized and catalyzed borohydrided for reversible hydrogen storage |
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS538393A (en) * | 1976-06-28 | 1978-01-25 | Raffinage Cie Francaise | Store*manufacture and application of bonded hydrogen |
JP2001519312A (ja) * | 1997-10-10 | 2001-10-23 | マクギル ユニバーシティ | 複合体アルカリ金属水素化物の製造方法 |
JP2004196634A (ja) * | 2002-12-20 | 2004-07-15 | Honda Motor Co Ltd | 水素貯蔵・放出システムに用いられる水素化物粉末 |
JP2005186058A (ja) * | 2003-12-03 | 2005-07-14 | Toyota Central Res & Dev Lab Inc | マグネシウム系水素吸蔵材料およびリチウム系水素吸蔵材料 |
JP2007076979A (ja) * | 2005-09-16 | 2007-03-29 | Tohoku Univ | 水素化・脱水素化反応速度の促進方法 |
JP2007117989A (ja) * | 2005-09-27 | 2007-05-17 | Toyota Central Res & Dev Lab Inc | 水素貯蔵材料及びその製造方法 |
WO2009062850A1 (de) * | 2007-11-16 | 2009-05-22 | Gkss-Forschungszentrum Geesthacht Gmbh | Wasserstoff speichernde kompositmaterialien |
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JP2011005485A (ja) * | 2009-06-16 | 2011-01-13 | Toyota Motor Engineering & Manufacturing North America Inc | 可逆的な水素貯蔵のための不安定化及び触媒された水素化ホウ素 |
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