Improvement of hydrogen storage property of three-component Mg(NH2)2-LiNH2-LiH composites by additives.

The three-component Mg(NH2)2-LiNH2-4LiH composite reversibly stores hydrogen exceeding 5 wt% at a temperature as low as 150 °C. In this work, a number of additives such as CeF4, CeO2, TiCl3, TiH2, NaH, KBH4 and KH are added to the Mg(NH2)2-LiNH2-4LiH composite in order to improve its kinetics, thermodynamics and cycling properties. Addition of 3 wt% of KH reduces the dehydrogenation onset temperature of the Mg(NH2)2-LiNH2-4LiH composite to below 90 °C without emission of NH3 during the whole dehydrogenation process up to 450 °C. Moreover, the dehydrogenation kinetics and cycling ability are remarkably enhanced upon KH-addition. The reaction model of the Mg(NH2)2-LiNH2-4LiH composite is altered upon KH-addition with the active molecule density improved by about 200 times. In addition, by optimization of the ratio of Mg2+ to Li+ in the Mg(NH2)2-LiNH2-LiH system, several novel composites, e.g., Mg(NH2)2-2LiNH2-5.9LiH-0.1KH and Mg(NH2)2-LiNH2-5.9LiH-0.1KH, with the hydrogen storage capacity exceeding 6 wt% without emission of NH3 below 250 °C are developed. Our study demonstrates that there are various undiscovered candidates with promising hydrogen storage properties in the three-component Li-Mg-N-H system.

[1]  M. Hirscher,et al.  Nanostructured materials for solid-state hydrogen storage : A review of the achievement of COST Action MP1103 , 2016 .

[2]  Lixian Sun,et al.  Synthesis of CsH and its effect on the hydrogen storage properties of the Mg(NH2)2-2LiH system , 2016 .

[3]  M. Paskevicius,et al.  Metal hydrides for concentrating solar thermal power energy storage , 2016 .

[4]  Torben R. Jensen,et al.  Complex and liquid hydrides for energy storage , 2016, Applied Physics A.

[5]  L. Ouyang,et al.  Tuning kinetics and thermodynamics of hydrogen storage in light metal element based systems – A review of recent progress , 2016 .

[6]  C. Milanese,et al.  A new potassium-based intermediate and its role in the desorption properties of the K-Mg-N-H system. , 2016, Physical chemistry chemical physics : PCCP.

[7]  Lars H. Jepsen,et al.  Synthesis and decomposition of Li3Na(NH2)4 and investigations of Li-Na-N-H based systems for hydrogen storage. , 2016, Physical chemistry chemical physics : PCCP.

[8]  H. Pan,et al.  Insights into the dehydrogenation reaction process of a K-containing Mg(NH2)2-2LiH system. , 2015, Dalton transactions.

[9]  Min Zhu,et al.  Enhanced hydrogen desorption property of MgH2 with the addition of cerium fluorides , 2015 .

[10]  Hai-Wen Li,et al.  A Li-Mg-N-H composite as H2 storage material: a case study with Mg(NH2)2-4LiH-LiNH2. , 2015, Chemical communications.

[11]  Weihua Wang,et al.  Symbiotic CeH2.73/CeO2 catalyst: A novel hydrogen pump , 2014 .

[12]  Rui-jun Ma,et al.  Superior dehydrogenation/hydrogenation kinetics and long-term cycling performance of K and Rb cocatalyzed Mg(NH(2))(2)-2LiH system. , 2014, ACS applied materials & interfaces.

[13]  H. Pan,et al.  High-temperature failure behaviour and mechanism of K-based additives in Li–Mg–N–H hydrogen storage systems , 2014 .

[14]  Lars H. Jepsen,et al.  Complex hydrides for hydrogen storage - New perspectives , 2014 .

[15]  Lars H. Jepsen,et al.  Boron-nitrogen based hydrides and reactive composites for hydrogen storage , 2014 .

[16]  Tengfei Zhang,et al.  A metal-oxide catalyst enhanced the desorption properties in complex metal hydrides , 2014 .

[17]  H. Pan,et al.  Compositional effects on the hydrogen storage properties of Mg(NH2)2-2LiH-xKH and the activity of KH during dehydrogenation reactions. , 2014, Dalton transactions.

[18]  Chu Liang,et al.  Solid-Solid heterogeneous catalysis: the role of potassium in promoting the dehydrogenation of the Mg(NH(2))(2)/2 LiH composite. , 2013, ChemSusChem.

[19]  H. Cao,et al.  Releasing 9.6 wt% of H2 from Mg(NH2)2-3LiH-NH3BH3 through mechanochemical reaction , 2013 .

[20]  H. Pan,et al.  Improved hydrogen-storage thermodynamics and kinetics for an RbF-doped Mg(NH2)2-2 LiH system. , 2013, Chemistry, an Asian journal.

[21]  Ping Chen,et al.  Amides and borohydrides for high-capacity solid-state hydrogen storage—materials design and kinetic improvements , 2013 .

[22]  Chu Liang,et al.  Understanding the role of K in the significantly improved hydrogen storage properties of a KOH-doped Li–Mg–N–H system , 2013 .

[23]  Ping Chen,et al.  Effects of Al-based additives on the hydrogen storage performance of the Mg(NH2)2-2LiH system. , 2013, Dalton transactions.

[24]  H. Pan,et al.  Improved hydrogen storage kinetics of the Li-Mg-N-H system by addition of Mg(BH4)2. , 2013, Dalton transactions.

[25]  J. Gu,et al.  Synergetic effects of in situ formed CaH2 and LiBH4 on hydrogen storage properties of the Li-Mg-N-H system. , 2013, Chemistry, an Asian journal.

[26]  C. Li,et al.  Metathesis Reaction-Induced Significant Improvement in Hydrogen Storage Properties of the KF-Added Mg(NH2)2–2LiH System , 2013 .

[27]  H. Pan,et al.  Hydrogen sorption from the Mg(NH2)2-KH system and synthesis of an amide-imide complex of KMg(NH)(NH2). , 2011, ChemSusChem.

[28]  T. Kiyobayashi,et al.  Cyclic properties and ammonia by-product emission of Li/MgNH hydrogen storage material , 2011 .

[29]  R. Ahuja,et al.  Potassium-modified Mg(NH2)2/2 LiH system for hydrogen storage. , 2009, Angewandte Chemie.

[30]  K. Luo,et al.  Size-dependent kinetic enhancement in hydrogen absorption and desorption of the Li-Mg-N-H system. , 2009, Journal of the American Chemical Society.

[31]  T. Kiyobayashi,et al.  Simultaneous determination of ammonia emission and hydrogen capacity variation during the cyclic testing for LiNH2-LiH hydrogen storage system , 2008 .

[32]  Christopher Wolverton,et al.  A self-catalyzing hydrogen-storage material. , 2008, Angewandte Chemie.

[33]  R. Ahuja,et al.  Thermodynamic analysis of hydrogen sorption reactions in Li–Mg–N–H systems , 2008 .

[34]  Yongfeng Liu,et al.  Structural and Compositional Changes during Hydrogenation/Dehydrogenation of the Li−Mg−N−H System , 2007 .

[35]  Christopher M Wolverton,et al.  First‐Principles Determination of Multicomponent Hydride Phase Diagrams: Application to the Li‐Mg‐N‐H System , 2007 .

[36]  Zhigang Zak Fang,et al.  Potential of Binary Lithium Magnesium Nitride for Hydrogen Storage Applications , 2007 .

[37]  Allan Walton,et al.  A mechanism for non-stoichiometry in the lithium amide/lithium imide hydrogen storage reaction. , 2007, Journal of the American Chemical Society.

[38]  K. Murata,et al.  Hydrogen release from Mg(NH2)2-MgH2 through mechanochemical reaction. , 2006, The journal of physical chemistry. B.

[39]  David S Sholl,et al.  Identification of destabilized metal hydrides for hydrogen storage using first principles calculations. , 2006, The journal of physical chemistry. B.

[40]  H. Fujii,et al.  Hydrogen storage properties in Ti catalyzed Li–N–H system , 2005 .

[41]  Ping-Ou Chen,et al.  Thermodynamic and kinetic investigations of the hydrogen storage in the Li–Mg–N–H system , 2005 .

[42]  S. Orimo,et al.  Synthesis and dehydriding studies of Mg–N–H systems , 2004 .

[43]  Weifang Luo,et al.  (LiNH2-MgH2): a viable hydrogen storage system , 2004 .

[44]  Jianjiang Hu,et al.  Ternary Imides for Hydrogen Storage , 2004 .

[45]  S. Hino,et al.  New Metal−N−H System Composed of Mg(NH2)2 and LiH for Hydrogen Storage , 2004 .

[46]  K. L. Tan,et al.  Interaction of hydrogen with metal nitrides and imides , 2002, Nature.

[47]  Tetsuo Sakai,et al.  Reversible Hydrogen Storage via Titanium-Catalyzed LiAlH4 and Li3AlH6 , 2001 .

[48]  B. Bogdanovic,et al.  Ti-doped alkali metal aluminium hydrides as potential novel reversible hydrogen storage materials , 1997 .

[49]  K. Buschow,et al.  Phase relations and hydrogen absorption in the lanthanum-nickel system , 1972 .

[50]  K. Buschow,et al.  Intermetallic compounds in the system samarium-cobalt , 1968 .

[51]  B. Achar,et al.  Numerical Data for Some Commonly Used Solid State Reaction Equations , 1966 .

[52]  H. E. Kissinger Reaction Kinetics in Differential Thermal Analysis , 1957 .

[53]  B. Dong,et al.  Improved dehydrogenation properties of the LiNH2–LiH system by doping with alkali metal hydroxide , 2015 .

[54]  J. Reilly,et al.  Formation and properties of iron titanium hydride , 1974 .