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Bimetallic borohydrides: hydrogen storage and superionic conductivity.

Applicant Cerny Radovan
Number 131811
Funding scheme Project funding (Div. I-III)
Research institution Laboratoire de Cristallographie Université de Genève
Institution of higher education University of Geneva - GE
Main discipline Condensed Matter Physics
Start/End 01.10.2010 - 30.09.2013
Approved amount 165'020.00
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All Disciplines (3)

Discipline
Condensed Matter Physics
Inorganic Chemistry
Material Sciences

Keywords (8)

metal hydride; ionic conductor; Metal hydride; Borohydride; Hydrogen storage; Ionic conductivity; Powder diffraction; Crystal structure

Lay Summary (French)

Lead
L'hydrogène est reconnu comme un futur vecteur énergétique. Un défi majeur est le développement de moyens efficaces de stockage de l'hydrogène. Les borohydrures de métaux ont attiré beaucoup d'attention en raison de leur teneur en hydrogène extrêmement élevée et récemment aussi en raison de la conductivité ionique du lithium.
Lay summary

Contenu et objectifs du travail de recherche:

L'utilisation des borohydrures métalliques est entravée par leur stabilité thermique soit trop élevée soit trop base. L'idée de ce projet est de mélanger des borohydrures des métaux alcalins (très stable) avec des borohydrures des métaux de transition (instable) et produire des borohydrures bimétalliques pour ajuster leur domaine de la stabilité. Nous cherchons activement des nouvelles composées et caractérisons leur structure cristalline, stabilité thermique et conductivité ionique.

 

Contexte scientifique et social du projet de recherche:

Nous avons réussi de synthétisé plusieurs nouveaux borohydrures bi- et tri-métalliques avec la stabilité optimale et avec la conductivité ionique du lithium qui peut être optimisée par la suite en introduisant des lacunes sur les sites atomiques. Nous avons découvert des nouvelles familles des borohydrures tell que les pérovskites qui ouvrent la porte aux autres applications de ces composées tell que la luminescence et la photovoltaïque.

Direct link to Lay Summary Last update: 27.09.2013

Responsible applicant and co-applicants

Employees

Name Institute

Publications

Publication
Impact of hydrogen absorption on crystal structure and magnetic properties of geometrically frustrated Nd2Ni2In
Mašková Silvie, Havela Ladislav, Daniš Stanislav, Llobet Anna, Nakotte Heinz, Kothapalli Karunakar, Černý Radovan, Kolomiets Aleksandre V. (2013), Impact of hydrogen absorption on crystal structure and magnetic properties of geometrically frustrated Nd2Ni2In, in Journal of Alloys and Compounds, 566, 22-30.
Novel alkali earth borohydride Sr(BH4)2 and borohydride-chloride Sr(BH4)Cl
Ravnsbæk Dorthe B., Nickels Elizabeth Anne, Černý Radovan, Olesen C. H., David William I F, Edwards Peter Phillip, Filinchuk Yaroslav, Jensen Torben René (2013), Novel alkali earth borohydride Sr(BH4)2 and borohydride-chloride Sr(BH4)Cl, in Inorganic Chemistry, 52(19), 10877-10885.
Trimetallic borohydride Li3MZn5(BH4) 15 (M = Mg, Mn) containing two weakly interconnected frameworks
Černý, Schouwink Pascal, Sadikin Yolanda, Stare Katarina, Smrčok Ľubomír, Richter Bo, Jensen Torben René (2013), Trimetallic borohydride Li3MZn5(BH4) 15 (M = Mg, Mn) containing two weakly interconnected frameworks, in Inorganic Chemistry, 52(17), 9941-9947.
Bimetallic Borohydrides in the System M(BH4)(2)-KBH4 (M = Mg, Mn): On the Structural Diversity
Schouwink P, D'Anna V, Ley MB, Daku LML, Richter B, Jensen TR, Hagemann H, Cerny R (2012), Bimetallic Borohydrides in the System M(BH4)(2)-KBH4 (M = Mg, Mn): On the Structural Diversity, in JOURNAL OF PHYSICAL CHEMISTRY C, 116(20), 10829-10840.
Mechano-chemical synthesis of manganese borohydride (Mn(BH 4)2) and inverse cubic spinel (Li2MnCl 4) in the (nLiBH4 + MnCl2) (n = 1, 2, 3, 5, 9 and 23) mixtures and their dehydrogenation behavior
Varin Robert A., Zbroniec Leszek, Polański Marek, Filinchuk Yaroslav, Černy Radovan Jr (2012), Mechano-chemical synthesis of manganese borohydride (Mn(BH 4)2) and inverse cubic spinel (Li2MnCl 4) in the (nLiBH4 + MnCl2) (n = 1, 2, 3, 5, 9 and 23) mixtures and their dehydrogenation behavior, in International Journal of Hydrogen Energy, 37(21), 16056-16069.
New CeMgCo4 and Ce2MgCo9 compounds: Hydrogenation properties and crystal structure of hydrides
Denys RV, Riabov AB, Cerny R, Koval'chuk IV, Zavaliy IY (2012), New CeMgCo4 and Ce2MgCo9 compounds: Hydrogenation properties and crystal structure of hydrides, in JOURNAL OF SOLID STATE CHEMISTRY, 187, 1-6.
Potassium Zinc Borohydrides Containing Triangular [Zn(BH4)(3)](-) and Tetrahedral [Zn(BH4)(x)Cl4-x](2-) Anions
Cerny R, Ravnsbaek DB, Schouwink P, Filinchuk Y, Penin N, Teyssier J, Smrcok L, Jensen TR (2012), Potassium Zinc Borohydrides Containing Triangular [Zn(BH4)(3)](-) and Tetrahedral [Zn(BH4)(x)Cl4-x](2-) Anions, in JOURNAL OF PHYSICAL CHEMISTRY C, 116(1), 1563-1571.
Complex inorganic structures from powder diffraction: Case of tetrahydroborates of light metals
Černy Radovan Jr, Filinchuk Yaroslav (2011), Complex inorganic structures from powder diffraction: Case of tetrahydroborates of light metals, in Zeitschrift fur Kristallographie, 226(12), 882-891.
Crystal structure of the novel Mg3MnNi2D3-x interstitial deuteride
Denys RV, Riabov AR, Berezovets VV, Koval'chuk IV, Cerny R, Zavaliy IY (2011), Crystal structure of the novel Mg3MnNi2D3-x interstitial deuteride, in INTERMETALLICS, 19(10), 1563-1566.
MgxMn(1-x)(BH4)(2) (x=0-0.8), a cation solid solution in a bimetallic borohydride
Cerny R, Penin N, D'Anna V, Hagemann H, Durand E, Ruzicka J (2011), MgxMn(1-x)(BH4)(2) (x=0-0.8), a cation solid solution in a bimetallic borohydride, in ACTA MATERIALIA, 59(13), 5171-5180.
Mitigation of Hydrogen Capacity Losses during Pressure Cycling of the Li3N-H System by the Addition of Nitrogen
Lamb J, Chandra D, Chien WM, Phanon D, Penin N, Cerny R, Yvon K (2011), Mitigation of Hydrogen Capacity Losses during Pressure Cycling of the Li3N-H System by the Addition of Nitrogen, in JOURNAL OF PHYSICAL CHEMISTRY C, 115(29), 14386-14391.
Novel sodium aluminium borohydride containing the complex anion [Al(BH4{,}Cl)4]-
Lindemann Inge, Ferrer Roger Domenech, Dunsch Lothar, Cerny Radovan, Hagemann Hans, D{'}Anna Vincenza, Filinchuk Yaroslav, Schultz Ludwig, Gutfleisch Oliver (2011), Novel sodium aluminium borohydride containing the complex anion [Al(BH4{,}Cl)4]-, in Faraday Discuss., 151, 231-242.
Powder diffraction methods for studies of borohydride-based energy storage materials
Ravnsbaek DB, Filinchuk Y, Cerny R, Jensen TR (2010), Powder diffraction methods for studies of borohydride-based energy storage materials, in ZEITSCHRIFT FUR KRISTALLOGRAPHIE, 225(12), 557-569.
Hydrogen absorption in RE2T2In compounds
Mašková Silvie, Kolomiets Aleksandre V., Havela Ladislav, Andreev A. V., Svoboda Pavel, Nakotte Heinz, Černý Radovan, Hydrogen absorption in RE2T2In compounds, in Journal of Alloys and Compounds.

Collaboration

Group / person Country
Types of collaboration
University of Ekaterinburg Russia (Europe)
- in-depth/constructive exchanges on approaches, methods or results
Institut of Inorganic Chemistry, Slovak Academy of Sciences Slovakia (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Academy of Sciences, Prague Czech Republic (Europe)
- in-depth/constructive exchanges on approaches, methods or results
Dpt. Physical Chemistry, University of Geneva Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
IFW Dresden Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Université catholique Louvain Belgium (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
University of Aarhus Denmark (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
Hydrogen Interactions in Energy Storage, Gordon Research Conference Poster 5 posters 15.07.2013 Lucca, Italy Cerny Radovan; Schouwink Pascal;
Hydrogen in Metals and Compounds, Gordon Research Seminar Talk given at a conference Borohydride Perovskites 14.07.2013 Lucca, Italy Schouwink Pascal;
MRS spring meeting Talk given at a conference Borohydride Perovskites - Analogies and Anomalies 23.05.2013 Strasbourg, France Schouwink Pascal;
Advances in Powder Diffraction IV Talk given at a conference Crystal structures from powder diffraction, principles, difficulties and progress 22.04.2013 Gaithersburg, United States of America Cerny Radovan;
13th EPDIC Talk given at a conference « Structure solution of extended solids, principles and examples », and « Complex hydrides: When powder diffraction reaches its limits » 15.10.2012 Grenoble, France Schouwink Pascal; Cerny Radovan;
Metal Hydrides Int. conf. Talk given at a conference Trimetallics: A new chapter in borohydride chemistry 10.10.2012 Kyoto, Japan Schouwink Pascal;
Annual meeting of the SSCr. Poster Novel Trimetallic Borohydrides: joint effort of experiment and theory 20.06.2012 Zurich, Switzerland Cerny Radovan;
Annual meeting of the Czech and Slovak cryst. Soc. Talk given at a conference « Crystal structure determination from powder diffraction: case of non-molecular compounds ». 11.06.2012 Klatovy, Czech Republic Cerny Radovan;
Seminar at the Inorganic Chemistry Dpt., University, Göteborg Individual talk Exciting Crystal Chemistry of Metal Borohydrides: Highlights and Pitfalls of Powder Diffraction and of DFT 24.05.2012 Goteborg, Sweden Cerny Radovan;
Seminar at the Inorganic Chemistry Dpt., University, Como Individual talk « Chemical storage of hydrogen in metal hydrides » and « Exciting Crystal Chemistry of Metal Borohydrides: Highlights and Pitfalls of Powder Diffraction and of DFT » 20.04.2012 Como, Italy Cerny Radovan;
Ecole doctorale de physique, EPFL Individual talk Microstructure and Pair Distribution Function analysis 06.02.2012 Lausanne, Switzerland Cerny Radovan;
Seminar at the Technical University Individual talk Borohydrides: from crystal chemistry to applications 10.01.2012 Vienna, Austria Schouwink Pascal;
Annual meeting of the SSCr Talk given at a conference Exciting Crystal Chemistry of Bimetallic Borohydrides 16.09.2011 Bern, Switzerland Schouwink Pascal; Cerny Radovan;
22nd IUCr Congress Poster Exciting Crystal Chemistry of Mixed Metal-Borohydrides 22.08.2011 Madrid, Spain, Spain Schouwink Pascal;
44th Erice School Talk given at a conference « Inorganic materials » and « FOX - Free Objects for Xtallography ». 02.06.2011 Erice. Italy, Italy Cerny Radovan;
41st Danish Crystallographic Meeting Talk given at a conference « Powder Diffraction Today: From High Resolution Data and Complex Structures to Low Quality Data and Local Structures » and « FOX - Free Objects for Xtallography ». 30.05.2011 Aarhus, Denmark Cerny Radovan;
Seminaire on Max Planck Institute for Chemical Physics of Solids Individual talk Surprising crystal chemistry of borohydrides from powder diffraction 12.10.2010 Dresden, Germany Cerny Radovan;


Associated projects

Number Title Start Funding scheme
144969 Digital Laue camera 01.10.2013 R'EQUIP
107916 Local structure and lattice defects in metal hydrides and hydrogen absorbing intermetallic compounds 01.09.2005 Project funding (Div. I-III)
122123 Local order in GdFe2 and LaNi5 hydrides and in new series of borohydrides 01.10.2008 Project funding (Div. I-III)
122123 Local order in GdFe2 and LaNi5 hydrides and in new series of borohydrides 01.10.2008 Project funding (Div. I-III)
53847 Inorganic crystal structures from powder diffraction by a model building approach 01.10.1998 Project funding (Div. I-III)
149218 Polymetallic borohydrides for hydrogen storage and lithium batteries: crystal engineering. 01.10.2013 Project funding (Div. I-III)
152397 Metal-Hydride Organic Frameworks (HOF)-new solids for gas adsorption and separation 01.04.2014 SCOPES

Abstract

The aim of the project is the development of new materials - bimetallic borohydrides - as hydrogen storage materials, and as superionic conductors. Hydrogen storage for mobile applications is still an open question. The cryogenic storage, compressed gas, chemical and physical storage are four directions intensively studied. The chemical storage, by chemical bonding in metal hydrides, seems to have the highest chance to follow the demanding application targets like for example those specified by US Dpt. of Energy: high volumetric and weight hydrogen capacities, hydrogen release temperatures, reversibility, low cost, safety. Among the materials used for hydrogen storage the compounds of light and/or transition metal M (1-4 period), boron and hydrogen, borohydrides, also called tetrahydridoborates, are very attractive due to their composition from light atoms, and high hydrogen content. However, the reversibility, and especially the hydrogen release temperatures Tdec between 60 and 120 deg C, are hard to achieve. Borohydrides are largely ionic compounds with a general formula M(BH4)n containing metallic cation and [BH4]- anion. Most of alkaline earth and alkaline metal borohydrides are too stable. On the other hand most borohydrides of 3d-metals are unstable and volatile. The tuning of the thermodynamic properties of borohydride-based hydrogen storage materials by the preparation of bimetallic (alkaline or alkaline earth and transition-metal) borohydrides has been suggested. We will follow this idea in our project, because we have already shown on the new compound LiSc(BH4)4 that it is a good direction, and we have good experience with borohydride preparation by mechanochemical synthesis - ball milling from alkaline metal borohydrides, and transition metal halides, both easy available. The method has the advantage of easy control of the synthesis product composition by milling of starting products in different stoichiometric ratios. In the project we will concentrate on a prospective work, investigation of different phase diagrams, and full crystal chemistry characterization by powder diffraction method, the field where we belong among the leaders in the methodology development (program Fox). We expect to find a material with suitable Tdec, which release only hydrogen without diborane (B2H6) evolution. To achieve that we have a possibility to tune the materials property not only by mixing the cations, but also the anions: substitution of [BH4]- by halide anions like Cl-. It has been shown that anion mixing modifies the thermal stability of borohydride phases.Besides he hydrogen storage properties we will search also for the superionic conductivity based on high mobility of Li+ cations as it was observed for HT hexagonal phase of LiBH4. It is possible to stabilize this superionic phase by anionic substitution using halides. The material with so high Li+ cations based electrical conductivity as of the order of 10-3 Scm-1 is of interest for applications in lithium batteries like solid electrolytes or anode/electrolyte interface. We expect to find the superionic properties also in other lithium containing borohydrides like LiSc(BH4)4 with the help of anionic substitution which modifies not only the stability of non-ambient phases, but also the anion/cation packing in the crystal.In this project we want to continue the research on borohydrides started in October 2009 within the second part of the SNSF project no. 200020-122123. We will also follow the methodology of ab-initio crystal structure determination from powder diffraction data as developed within our project no. 21-53847.98 (program Fox). We will also use, when needed, the expertise in the study of local order in disordered structures by the Pair Distribution Function (PDF) analysis, which we have developed within our projects no. 200021-107916 and 200020-122123.The synthesis work will be done in our laboratory by ball-milling at ambient and cryogenic temperatures. The structural analysis including temperature or pressure dependent studies will be done at powder diffraction installations at world leading synchrotron sources, such as Swiss-Norwegian Beamline (SNBL) at the ESRF in Grenoble or Swiss Light Source at the PSI Villigen. Since 2002 we have developed a very intense and successful collaboration between the University of Geneva (R. Cerný, H. Hagemann) and SNBL Grenoble (Y. Filinchuk) which is at the origin of 9 light metal borohydrides from 14 fully characterized up to now, including LiBH4 with highest hydrogen storage capacity (more than 18 wt.% of hydrogen), and Mg(BH4)2, the most complex one (55 independent atoms). We are convinced that such top rank research is important for a good image of Swiss science. The presented project is an active part of these studies, and follows the work that started eight years ago.
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