Project

Back to overview

Polymetallic borohydrides for hydrogen storage and lithium batteries: crystal engineering.

Applicant Cerny Radovan
Number 149218
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 01.10.2013 - 30.09.2016
Approved amount 210'000.00
Show all

All Disciplines (3)

Discipline
Condensed Matter Physics
Inorganic Chemistry
Material Sciences

Keywords (5)

Powder Diffraction; Borohydride; Solid electrolyte; Hydrogen storage; Lithium battery

Lay Summary (French)

Lead
Un défi majeur pour les applications des borohydrures de métaux pour le stockage de l'hydrogène et pour les batteries à lithium est le développement des matériaux avec une capacité élevé, propriétés thermodynamique favorable, avec une bon duré de vie, pas chers et sures.
Lay summary
Contenu et objectifs du travail de recherche

Dans le projet précèdent nous avons réussi synthétisé plusieurs nouveaux borohydrures bi- et tri-métalliques avec la stabilité optimale et avec la conductivité ionique du lithium qui peut être optimisée en introduisant des lacunes sur les sites atomiques. Dans le projet actuel nous voulons poursuivre ces études avec des nouvelles familles des borohydrures tell que les pérovskites, spinel et garnet.

Contexte scientifique et social du projet de recherche

Notre recherche va permettre comprendre les règles qui contrôlent la stabilité des borohydrures, ajuster la stabilité dans le domaine de températures voulu et même prédire des nouveaux borohydrures en utilisant leurs analogie avec d'autre familles des composées inorganique tell que des oxydes. Ces nouveaux borohydrures vont trouver leur utilité dans le stockage de l'énergie en forme de l'hydrogène pour les piles à combustible et en forme de l'électricité dans les batteries au lithium, sodium ou magnésium. Les borohydrures - pérovskite ouvrent aussi la porte aux autres applications tell que la luminescence et la photovoltaïque.

Direct link to Lay Summary Last update: 04.10.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Fast ion conduction in garnet-type metal borohydrides Li3K3Ce2(BH4)12 and Li3K3La2(BH4)12
Brighi M., Schouwink P., Sadikin Y., Černý R., Brighi M., Schouwink P., Sadikin Y., Černý R. (2016), Fast ion conduction in garnet-type metal borohydrides Li3K3Ce2(BH4)12 and Li3K3La2(BH4)12, in Journal of Alloys and Compounds , 662, 388-395.
From M(BH 4 ) 3 (M = La, Ce) Borohydride Frameworks to Controllable Synthesis of Porous Hydrides and Ion Conductors
Ley Morten Brix, Jørgensen Mathias, Černý Radovan, Filinchuk Yaroslav, Jensen Torben R., Ley Morten Brix, Jørgensen Mathias, Černý Radovan, Filinchuk Yaroslav, Jensen Torben R. (2016), From M(BH 4 ) 3 (M = La, Ce) Borohydride Frameworks to Controllable Synthesis of Porous Hydrides and Ion Conductors, in Inorganic Chemistry, 55(19), 9748-9756.
Halide Free M(BH4)2 (M = Sr, Ba, and Eu) Synthesis, Structure, and Decomposition
Sharma Manish, Didelot Emilie, Spyratou Alexandra, Lawson Daku Latévi Max, Černý Radovan, Hagemann Hans, Sharma Manish, Didelot Emilie, Spyratou Alexandra, Lawson Daku Latévi Max, Černý Radovan, Hagemann Hans (2016), Halide Free M(BH4)2 (M = Sr, Ba, and Eu) Synthesis, Structure, and Decomposition, in Inorganic Chemistry, 55(14), 7090-7097.
High-Pressure Study of Mn(BH4)2 Reveals a Stable Polymorph with High Hydrogen Density
Tumanov Nikolay A., Roedern Elsa, Łodziana Zbigniew, Nielsen Dorrit B., Jensen Torben R., Talyzin Alexandr V., Černý Radovan, Chernyshov Dmitry, Dmitriev Vladimir, Palasyuk Taras, Filinchuk Yaroslav, Tumanov Nikolay A., Roedern Elsa, Łodziana Zbigniew, Nielsen Dorrit B., Jensen Torben R., Talyzin Alexandr V., Černý Radovan, Chernyshov Dmitry, Dmitriev Vladimir, Palasyuk Taras, Filinchuk Yaroslav (2016), High-Pressure Study of Mn(BH4)2 Reveals a Stable Polymorph with High Hydrogen Density, in Chemistry of Materials, 28(1), 274-283.
Structural and magnetocaloric properties of novel gadolinium borohydrides
Schouwink Pascal, Didelot Emilie, Lee Young-Su, Mazet Thomas, Černý Radovan, Schouwink Pascal, Didelot Emilie, Lee Young-Su, Mazet Thomas, Černý Radovan (2016), Structural and magnetocaloric properties of novel gadolinium borohydrides, in Journal of Alloys and Compounds , 664, 378-384.
Synthesis and thermal stability of perovskite alkali metal strontium borohydrides
Moller Kasper T., Ley Morten B., Schouwink Pascal, Cerny Radovan, Jensen Torben R., Moller Kasper T., Ley Morten B., Schouwink Pascal, Cerny Radovan, Jensen Torben R. (2016), Synthesis and thermal stability of perovskite alkali metal strontium borohydrides, in Dalton Trans., 45, 831-840.
Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth
Sadikin Yolanda, Stare Katarina, Schouwink Pascal, Ley Morten Brix, Jensen Torben R., Meden Anton, Černý Radovan, Sadikin Yolanda, Stare Katarina, Schouwink Pascal, Ley Morten Brix, Jensen Torben R., Meden Anton, Černý Radovan (2015), Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth, in Journal of Solid State Chemistry , 225(0), 231-239.
Ammine Calcium and Strontium Borohydrides: Syntheses, Structures, and Properties
Jepsen Lars H., Lee Young-Su, Cerny Radovan, Sarusie Ram S., Cho Young Whan, Besenbacher Flemming, Jensen Torben R., Jepsen Lars H., Lee Young-Su, Cerny Radovan, Sarusie Ram S., Cho Young Whan, Besenbacher Flemming, Jensen Torben R. (2015), Ammine Calcium and Strontium Borohydrides: Syntheses, Structures, and Properties, in ChemSusChem, 8(20), 3472-3482.
Di-hydrogen contact induced lattice instabilities and structural dynamics in complex hydride perovskites
Schouwink P, Hagemann H, Embs J P, D’Anna V, Černý R, Schouwink P, Hagemann H, Embs J P, D’Anna V, Černý R (2015), Di-hydrogen contact induced lattice instabilities and structural dynamics in complex hydride perovskites, in Journal of Physics: Condensed Matter, 27(26), 265403-265403.
Experimental observation of polymerization from to in mixed-anion (A = Rb+, Cs+)
Schouwink P., Sadikin Y., van Beek W., Černý R., Schouwink P., Sadikin Y., van Beek W., Černý R. (2015), Experimental observation of polymerization from to in mixed-anion (A = Rb+, Cs+), in International Journal of Hydrogen Energy , 40(34), 10902-10907.
Flux-assisted single crystal growth and heteroepitaxy of perovskite-type mixed-metal borohydrides
Schouwink Pascal, Ramel Adrien, Giannini Enrico, Cerny Radovan, Schouwink Pascal, Ramel Adrien, Giannini Enrico, Cerny Radovan (2015), Flux-assisted single crystal growth and heteroepitaxy of perovskite-type mixed-metal borohydrides, in CrystEngComm, 17, 2682-2689.
Increasing Hydrogen Density with the Cation-Anion Pair BH4-NH4+ in Perovskite-Type NH4Ca(BH4)3
Schouwink Pascal, Morelle Fabrice, Sadikin Yolanda, Filinchuk Yaroslav, Cerny Radovan, Schouwink Pascal, Morelle Fabrice, Sadikin Yolanda, Filinchuk Yaroslav, Cerny Radovan (2015), Increasing Hydrogen Density with the Cation-Anion Pair BH4-NH4+ in Perovskite-Type NH4Ca(BH4)3, in Energies, 8(8), 8286-8299.
Isotope Exchange Reactions in Ca(BH4)2
Sharma Manish, Sethio Daniel, D’Anna Vincenza, Fallas Juan C., Schouwink Pascal, Černý Radovan, Hagemann Hans, Sharma Manish, Sethio Daniel, D’Anna Vincenza, Fallas Juan C., Schouwink Pascal, Černý Radovan, Hagemann Hans (2015), Isotope Exchange Reactions in Ca(BH4)2, in The Journal of Physical Chemistry C, 119(1), 29-32.
Nuclear Magnetic Resonance Study of Atomic Motion in Bimetallic Perovskite-Type Borohydrides ACa(BH4)3 (A = K, Rb, or Cs)
Skoryunov Roman V., Soloninin Alexei V., Babanova Olga A., Skripov Alexander V., Schouwink Pascal, Černý Radovan, Skoryunov Roman V., Soloninin Alexei V., Babanova Olga A., Skripov Alexander V., Schouwink Pascal, Černý Radovan (2015), Nuclear Magnetic Resonance Study of Atomic Motion in Bimetallic Perovskite-Type Borohydrides ACa(BH4)3 (A = K, Rb, or Cs), in The Journal of Physical Chemistry C, 119(34), 19689-19696.
Superionic Conduction of Sodium and Lithium in Anion-Mixed Hydroborates Na3BH4B12H12 and (Li0.7Na0.3)3BH4B12H12
Sadikin Yolanda, Brighi Matteo, Schouwink Pascal, Cerny Radovan, Sadikin Yolanda, Brighi Matteo, Schouwink Pascal, Cerny Radovan (2015), Superionic Conduction of Sodium and Lithium in Anion-Mixed Hydroborates Na3BH4B12H12 and (Li0.7Na0.3)3BH4B12H12, in Advanced Energy Materials, 1501016.
Synthesis, structure and dehydrogenation of zirconium borohydride octaammoniate
Huang Jianmei, Tan Yingbin, Su Jiahao, Gu Qinfen, Cerny Radovan, Ouyang Liuzhang, Sun Dalin, Yu Xuebin, Zhu Min, Huang Jianmei, Tan Yingbin, Su Jiahao, Gu Qinfen, Cerny Radovan, Ouyang Liuzhang, Sun Dalin, Yu Xuebin, Zhu Min (2015), Synthesis, structure and dehydrogenation of zirconium borohydride octaammoniate, in Chem. Commun., 51, 2794-2797.
The crystal chemistry of inorganic metal boro{\-}hydrides and their relation to metal oxides
Černý Radovan, Schouwink Pascal, Černý Radovan, Schouwink Pascal (2015), The crystal chemistry of inorganic metal boro{\-}hydrides and their relation to metal oxides, in Acta Crystallographica Section B, 71(6), 619-640.
Trends in Syntheses, Structures, and Properties for Three Series of Ammine Rare-Earth Metal Borohydrides, M(BH4)3·nNH3 (M = Y, Gd, and Dy)
Jepsen Lars H., Ley Morten B., Černý Radovan, Lee Young-Su, Cho Young Whan, Ravnsbæk Dorthe, Besenbacher Flemming, Skibsted Jørgen, Jensen Torben R., Jepsen Lars H., Ley Morten B., Černý Radovan, Lee Young-Su, Cho Young Whan, Ravnsbæk Dorthe, Besenbacher Flemming, Skibsted Jørgen, Jensen Torben R. (2015), Trends in Syntheses, Structures, and Properties for Three Series of Ammine Rare-Earth Metal Borohydrides, M(BH4)3·nNH3 (M = Y, Gd, and Dy), in Inorganic Chemistry, 54(15), 7402-7414.
Borohydrides: from sheet to framework topologies
Schouwink P., Ley M. B., Jensen T. R., Smrcok L., Černý R., Schouwink P., Ley M. B., Jensen T. R., Smrcok L., Černý R. (2014), Borohydrides: from sheet to framework topologies, in Dalton Trans., 43, 7726-7733.
Complex Hydrides – When Powder Diffraction needs Help
Schouwink Pascal, Černý Radovan, Schouwink Pascal, Černý Radovan (2014), Complex Hydrides – When Powder Diffraction needs Help, in CHIMIA International Journal for Chemistry, 68(1), 38-44.
Novel solvates M(BH4)3S(CH3)2 and properties of halide-free M(BH4)3 (M = Y or Gd)
Ley Morten B., Paskevicius Mark, Schouwink Pascal, Richter Bo, Sheppard Drew A., Buckley Craig E., Jensen Torben R., Ley Morten B., Paskevicius Mark, Schouwink Pascal, Richter Bo, Sheppard Drew A., Buckley Craig E., Jensen Torben R. (2014), Novel solvates M(BH4)3S(CH3)2 and properties of halide-free M(BH4)3 (M = Y or Gd), in Dalton Trans., 43, 13333-13342.
Role of the Li+ node in the Li-BH4 substructure of double-cation tetrahydroborates
Schouwink Pascal, Smrcok Lubomir, Černý Radovan, Schouwink Pascal, Smrcok Lubomir, Černý Radovan (2014), Role of the Li+ node in the Li-BH4 substructure of double-cation tetrahydroborates, in Acta Crystallographica B, 70(5), 871-878.
Structure and properties of complex hydride perovskite materials
Schouwink Pascal, Ley Morten B., Tissot Antoine Michel, Hagemann Hans-Rudolf, Jensen Torben R., Smrčok Ľubomír, Černý Radovan, Schouwink Pascal, Ley Morten B., Tissot Antoine Michel, Hagemann Hans-Rudolf, Jensen Torben R., Smrčok Ľubomír, Černý Radovan (2014), Structure and properties of complex hydride perovskite materials, in Nature Communications, 5, 5706.
The First Halide-Free Bimetallic Aluminum Borohydride: Synthesis, Structure, Stability, and Decomposition Pathway
Dovgaliuk Iurii, Ban Voraksmy, Sadikin Yolanda, Černý Radovan, Aranda Lionel, Casati Nicola, Devillers Michel, Filinchuk Yaroslav, Dovgaliuk Iurii, Ban Voraksmy, Sadikin Yolanda, Černý Radovan, Aranda Lionel, Casati Nicola, Devillers Michel, Filinchuk Yaroslav (2014), The First Halide-Free Bimetallic Aluminum Borohydride: Synthesis, Structure, Stability, and Decomposition Pathway, in The Journal of Physical Chemistry C, 118(1), 145-153.

Collaboration

Group / person Country
Types of collaboration
Lubomir Smrcok, Academie des sciences, Bratislava Slovakia (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
H. Hagemann, Dpt. de Chimie Physique, Université de Genève Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
Zbigniew Lodziana/Academy of Sciences Poland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Alexander Skripov, Institute of Metal Physics, Russian Academy of Sciences, Ekaterinburg Russia (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Yaroslav Filinchuk, Université catholique de Louvain Belgium (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel
Torben Jensen, Université de 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
ECM 30 Poster Thermal Polymorphism and Decomposition of M(BH4)2 (M= Sr, Ba and Eu) 28.08.2016 Basel, Switzerland Cerny Radovan; Didelot Emilie;
ECM 30 Talk given at a conference Structure and magnetocaloric properties of Gadolinium borohydrides 28.08.2016 Basel, Switzerland Schouwink Pascal; Didelot Emilie; Cerny Radovan;
ECM 30 Poster Structural design principles for close packed Na and Li solid-electrolytes built from mixed anion borane lattices 28.08.2016 Basel, Switzerland Schouwink Pascal; Cerny Radovan;
ECM 30 Poster Anion Packing and Cation Mobility in Potential Solid Electrolytes Na2B12H12-xIx and (A1A2)B12H12 (A1 = Li, Na, A2 = Li, Na, K, Cs) 28.08.2016 Basel, Switzerland Schouwink Pascal; Cerny Radovan;
MH 2016 Talk given at a conference Hydroborates Design supported by Crystal Chemistry Concept 07.08.2016 Interlaken, Switzerland Cerny Radovan;
MH 2016 Talk given at a conference Structure and magnetocaloric properties of Gadolinium borohydrides 07.08.2016 Interlaken, Switzerland Didelot Emilie;
MH 2016 Talk given at a conference Anion Packing and Cation Mobility in Potential Solid Electrolytes Na2B12H12-xIx and (A1A2)B12H12(A1 = Li, Na, A2 = Li, Na, K, Cs) 07.08.2016 Interlaken, Switzerland Schouwink Pascal; Cerny Radovan;
MH2016 Talk given at a conference Lanthanide Emission and Photoluminescence Quantum Efficiency of Perovskite and Garnet-Type Metal Borohydrides 07.08.2016 Interlaken, Switzerland Cerny Radovan; Schouwink Pascal;
EPDIC 15 Talk given at a conference Designing hydroborates for battery materials and hydrogen storage using crystal chemistry knowledge of oxides 12.06.2016 Bari, Italy Cerny Radovan;
HydEM Talk given at a conference Crystal Chemistry of Metal Borohydrides 01.06.2016 Aarhus, Denmark Cerny Radovan;
2nd Cracow's meeting on concepts related to Energy Talk given at a conference Hydroborates Design supported by Crystal Chemistry Concept 24.05.2016 Cracow, Poland Cerny Radovan;
European Crystallographic Meeting 29 Talk given at a conference Complex metal hydrides: When powder diffraction needs help; Energy-related aspects of complex metal borohydrides and higher boranes: beyond hydrogen storage. 23.08.2015 Rovinj, Croatia Cerny Radovan; Schouwink Pascal;
Congress of the International Union of Crystallography Talk given at a conference Borohydride - Oxide Isomorphism in Design of Hydrogen Storage and Battery Materials 05.08.2014 Montreal, Canada Cerny Radovan; Schouwink Pascal;
Congress of the International Union of Crystallography Poster Phase transitions in borohydride perovskites 05.08.2014 Montreal, Canada Cerny Radovan; Schouwink Pascal;
Metal Hydrides Poster Nuclear Magnetic Resonance Study of Atomic Motion in New Bimetallic Perovskite-Type Borohydrides RbCa(BH4)3 and CsCa(BH4)3 20.07.2014 Manchester, Great Britain and Northern Ireland Schouwink Pascal; Cerny Radovan;
Metal Hydrides Talk given at a conference Mechanochemical synthesis of hydrides followed in situ by X-ray diffraction 20.07.2014 Manchester, Great Britain and Northern Ireland Schouwink Pascal; Cerny Radovan;
Metal Hydrides Talk given at a conference Borohydrides: Stabilizing Light Metal Frameworks 20.07.2014 Manchester, Great Britain and Northern Ireland Cerny Radovan; Schouwink Pascal;
Metal Hydrides Poster Reversible Isotope Exchange Reactions in Ca(BH4)2 20.07.2014 Manchester, Great Britain and Northern Ireland Cerny Radovan; Schouwink Pascal;
Metal Hydrides Poster Bimetallic Borohydrides Synthesized from Sr(BH4)2 and Alkali Metal Borohydrides 20.07.2014 Manchester, Great Britain and Northern Ireland Cerny Radovan; Schouwink Pascal;
Metal Hydrides Poster Structural Analysis of Possible Lithium Migration Paths in Borohydrides 20.07.2014 Manchester, Great Britain and Northern Ireland Cerny Radovan;
European Powder Diffraction Conference Talk given at a conference Borohydrides: in situ powder diffraction and Li-rich topologies 15.06.2014 Aarhus, Denmark Cerny Radovan; Schouwink Pascal;


Communication with the public

Communication Title Media Place Year
Print (books, brochures, leaflets) Mixed anion metal boranes for solid state Na and Li electrolytes International 2015
Print (books, brochures, leaflets) Structure and properties of complex hydride perovskite materials International 2015
Media relations: print media, online media La cristallographie sur le devant de la scène Le Journal de l'UNIGE Western Switzerland 2014
Media relations: radio, television Quelques facettes de la cristallographie RTS La 1ère Western Switzerland 2014

Associated projects

Number Title Start Funding scheme
172503 Mixed anion and cation hydroborates as solid electrolytes for all-solid-state batteries 01.08.2017 Project funding (Div. I-III)
131811 Bimetallic borohydrides: hydrogen storage and superionic conductivity. 01.10.2010 Project funding (Div. I-III)

Abstract

The project deals with two completely new classes of materials: (1) metal borohydrides with crystal structures of perovskites, spinels and garnets known from compact iono-covalent systems like oxides, and (2) sheet and porous framework metal borohydrides with underlying nets known from aluminosilicates and coordination polymers, but presenting also novel nets which have not yet been observed. The primary interest, hydrogen storage for mobile applications and ionic conductivity of lithium for battery applications will be supported by detailed crystal chemistry analysis including modern topology analysis of frameworks and sheets, by characterization of thermodynamic and electric properties, and by DFT calculations.
-