Nanoglassy oxides via mechanochemistry: the formation mechanism, the short-range structure, functional properties and the thermal stability

• Applicant: Dr. Vladimir Sepelák
• Subject Area: Solid State and Surface Chemistry, Material Synthesis ; Physical Chemistry of Solids and Surfaces, Material Characterisation
• Term: from 2015 to 2019
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 286123581

• Final Report Year: 2024

Final Report Abstract

Novel nanoglassy complex oxides of various structure types (pyroxene, mullite, perovskite, spinel, fluorite, garnet) are prepared via mechanochemical routes. The application of a variety of comprehensive spectroscopic techniques enables to provide detailed complementary atomic-scale insights into the nature of the local short-range disorder of nanostructured oxides. Interfacial regions of the as-prepared nanomaterials are found to exhibit various structural and magnetic disorder phenomena, including the distorted structural units, the mutually tilted polyhedra, the ruptured polyhedral bonds, the reduced oxygen coordination of metal cations, the cation anti-site disorder, oxygen vacancies, the random distribution of constituent cations over the available crystal sites, the noncolinear spin arrangement, and the collapse of the long-ranged magnetism. The mechanism of the mechanically driven formation reactions of nonequilibrium oxide phases is interpreted as being due to the impact-induced nucleation and growth processes, which are spatially confined to highly disordered and reactive regions. The far-from-equilibrium nanostructured oxides prepared via mechanochemistry are found to exhibit unique macroscopic functional properties that may not be attainable through conventional synthetic routes. The focus is given to clear-cut explanation of the interplay between the short-range nanostructure of nanooxides and their macroscopic magnetic and electrochemical behaviour. The range of thermal stability of nanoglassy oxides is determined by investigations of their response to changes in temperature.

Publications

• Electrochemical properties of spinel Li4Ti5O12 nanoparticles prepared via a low-temperature solid route. Journal of Solid State Electrochemistry, 20(10), 2673–2683.
  Senna, Mamoru; Fabián, Martin; Kavan, Ladislav; Zukalová, Markéta; Briančin, Jaroslav; Turianicová, Erika; Bottke, Patrick; Wilkening, Martin & Šepelák, Vladimír
  
• Structural characterization of (Bi1-xGdx)14W2O27(x= 0.00 and 0.05) synthesized via mechano-thermal treatment. Integrated Ferroelectrics, 174(1), 56-62.
  Santiago, R. T.; Vieira, D. S.; Biagio, R. L.; Camargo, V. G.; Machado, C. F. C.; Fabián, M.; da Silva, K. L. & Šepelák, V.
  
• Combined mechanochemical/thermal synthesis of microcrystalline pyroxene LiFeSi2O6 and one-step mechanosynthesis of nanoglassy LiFeSi2O6−based composite. Journal of Alloys and Compounds, 707, 310-314.
  Turianicová, Erika; Witte, Ralf; Da Silva, Klebson L.; Zorkovská, Anna; Senna, Mamoru; Hahn, Horst; Heitjans, Paul & Šepelák, Vladimír
  
• The milling effect on nickel ferrite particles studied using magnetization measurements and Mössbauer spectroscopy. Hyperfine Interactions, 239(1).
  Ushakov, M. V.; Oshtrakh, M. I.; Chukin, A. V.; Šepelák, V.; Felner, I. & Semionkin, V. A.
  
• Local structure analysis of Bi2(Ga1-Fe )4O9 mullite-type solid solutions synthesized via combination of ball milling and thermal treatment. Solid State Sciences, 82, 106-110.
  Santiago, Rafael T.; Fabián, Martin; Šepelák, Vladimír; Cotica, Luiz F.; Santos, Ivair A.; Machado, Carla C.F.; Hahn, Horst; Becker, Klaus D. & da Silva, Klebson L.
  
• Mechanochemical syntheses of LiFeGe2O6-based nanocomposite and novel nanoglassy LiFeTi2O6. Journal of Materials Science, 53(19), 13530-13537.
  Tóthová, Erika; Witte, Ralf; Hegedüs, Michal; Senna, Mamoru; Hahn, Horst; Heitjans, Paul & Šepelák, Vladimír
  
• Mechanochemically processed zinc ferrite nanoparticles: Evolution of structure and impact of induced cation inversion. Journal of Magnetism and Magnetic Materials, 465, 603-610.
  Harris, Vincent G. & Šepelák, Vladimir
  
• Evidence of Tetrahedrally Coordinated Nickel Cations in Nanostructured NiFe2O4. Journal of Nanoscience and Nanotechnology, 19(6), 3654-3657.
  Fabián, Martin; Harničárová, Marta; Valíček, Jan; Da Silva, Klebson L.; Hahn, Horst; Šepelák, Vladimír; Lesňák, Michal & Kušnerová, Milena
  
• Preface. Materials Today: Proceedings, 12(2019), 1-2.
  Shakhtshneider, Tatyana P.; Dudina, Dina V.; Lyakhov, Nikolay Z. & Šepelák, Vladimir
  
• A sustainable reaction process for phase pure LiFeSi2O6 with goethite as an iron source. Ceramics International, 46(10), 14894-14901.
  Skurikhina, O.; Senna, M.; Fabián, M.; Witte, R.; Tarasenko, R.; Tkáč, V.; Orendáč, M.; Kaňuchová, M.; Girman, V.; Harničárová, M.; Valíček, J.; Šepelák, V. & Tóthová, E.
  
• A novel high entropy spinel-type aluminate MAl2O4 (M = Zn, Mg, Cu, Co) and its lithiated oxyfluoride and oxychloride derivatives prepared by one-step mechanosynthesis. Zeitschrift für Physikalische Chemie, 236(6-8), 713-726.
  Porodko, Olena; Fabián, Martin; Kolev, Hristo; Lisnichuk, Maksym; Zukalová, Markéta; Vinarčíková, Monika; Girman, Vladimír; Da Silva, Klebson Lucenildo & Šepelák, Vladimír
  
• Disordered Gd6UO12-δ with the cation antisite defects prepared by a combined mechanochemical−thermal method. Journal of Nuclear Materials, 549, 152895.
  Darin, G.; Imakuma, K.; Santiago, R.T.; Da Silva, K.L.; Cótica, L.F.; Fabián, M.; Valíček, J.; Hahn, H. & Šepelák, V.
  
• High-entropy energy materials: challenges and new opportunities. Energy & Environmental Science, 14(5), 2883-2905.
  Ma, Yanjiao; Ma, Yuan; Wang, Qingsong; Schweidler, Simon; Botros, Miriam; Fu, Tongtong; Hahn, Horst; Brezesinski, Torsten & Breitung, Ben
  
• Mechanochemical synthesis of novel rutile-type high entropy fluorides for electrocatalysis. Journal of Materials Chemistry A, 9(14), 8998-9009.
  Sukkurji, Parvathy Anitha; Cui, Yanyan; Lee, Seunghwa; Wang, Kai; Azmi, Raheleh; Sarkar, Abhishek; Indris, Sylvio; Bhattacharya, Subramshu S.; Kruk, Robert; Hahn, Horst; Wang, Qingsong; Botros, Miriam & Breitung, Ben
  
• Nanostructure and magnetic anomaly of mechanosynthesized Ce1-xYxO2-δ (x ≤ 0.3) solid solutions. Journal of Physics and Chemistry of Solids, 148, 109673.
  Fabián, Martin; Menzel, Dirk; Yermakov, Anatoly Ye; Kolev, Hristo; Kaňuchová, Mária; Shi, Jianmin; Kováč, Jaroslav; Kostova, Nina; Da Silva, Klebson L.; Senna, Mamoru; Harničárová, Marta; Valíček, Jan; Hahn, Horst & Šepelák, Vladimír
  
• Suppression of the Cycloidal Spin Arrangement in BiFeO3 Caused by the Mechanically Induced Structural Distortion and Its Effect on Magnetism. Frontiers in Materials, 8.
  Da Silva, Klebson Lucenildo; Trautwein, Rafael Santiago; Da, Silva Rodolfo Bezerra; Fabián, Martin; Čižmár, Erik; Holub, Mariia; Skurikhina, Olha; Harničárová, Marta; Girman, Vladimír; Menzel, Dirk; Becker, Klaus Dieter; Hahn, Horst & Šepelák, Vladimír
  
• Unusual cation coordination in nanostructured mullites. Zeitschrift für Physikalische Chemie, 236(6-8), 697-712.
  Šepelák, Vladimir; Da Silva, Klebson Lucenildo; Trautwein, Rafael Santiago; Becker, Klaus Dieter & Hahn, Horst
  
• A Unique Mechanochemical Redox Reaction Yielding Nanostructured Double Perovskite Sr2FeMoO6 With an Extraordinarily High Degree of Anti-Site Disorder. Frontiers in Chemistry, 10.
  Tóthová, Erika; Düvel, André; Witte, Ralf; Brand, Richard A.; Sarkar, Abhishek; Kruk, Robert; Senna, Mamoru; Da Silva, Klebson Lucenildo; Menzel, Dirk; Girman, Vladimír; Hegedüs, Michal; Baláž, Matej; Makreski, Petre; Kubuki, Shiro; Kaňuchová, Mária; Valíček, Jan; Hahn, Horst & Šepelák, Vladimír
  
• Embracing disorder in solid-state batteries. Science, 378(6626), 1273-1274.
  Botros, Miriam & Janek, Jürgen
  
• High entropy fluorides as conversion cathodes with tailorable electrochemical performance. Journal of Energy Chemistry, 72, 342-351.
  Cui, Yanyan; Sukkurji, Parvathy Anitha; Wang, Kai; Azmi, Raheleh; Nunn, Alexandra M.; Hahn, Horst; Breitung, Ben; Ting, Yin-Ying; Kowalski, Piotr M.; Kaghazchi, Payam; Wang, Qingsong; Schweidler, Simon & Botros, Miriam
  
• Synthesis of perovskite-type high-entropy oxides as potential candidates for oxygen evolution. Frontiers in Energy Research, 10.
  Schweidler, Simon; Tang, Yushu; Lin, Ling; Karkera, Guruprakash; Alsawaf, Alaa; Bernadet, Lucile; Breitung, Ben; Hahn, Horst; Fichtner, Maximilian; Tarancón, Albert & Botros, Miriam
  
• Infrared and Raman spectroscopy investigations in mullite-type Bi2(FexGa1-x)4O9 polycrystals. Ferroelectrics, 611(1), 239-245.
  Macková, L.; Santiago, R. T.; Fabián, M.; da Silva, K. L.; Sato, F.; Becker, K. D.; Šepelák, V.; Cótica, L. F. & Santos, I. A.
  
• Mechanochemistry and Emerging Technologies for Sustainable Chemical Manufacturing. CRC Press.
  Colacino, Evelina & García, Felipe
  
• Editorial: Recent advances in the identification of stress-strain states of materials. Frontiers in Materials, 11.
  Harničárová, Marta; Valíček, Jan & Šepeľák, Vladimír
  
• High-entropy materials for energy and electronic applications. Nature Reviews Materials, 9(4), 266-281.
  Schweidler, Simon; Botros, Miriam; Strauss, Florian; Wang, Qingsong; Ma, Yanjiao; Velasco, Leonardo; Cadilha, Marques Gabriel; Sarkar, Abhishek; Kübel, Christian; Hahn, Horst; Aghassi-Hagmann, Jasmin; Brezesinski, Torsten & Breitung, Ben
  
• Influence of Grain Size on the Electrochemical Performance of Li7‐3xLa3Zr2AlxO12 Solid Electrolyte. Batteries & Supercaps, 7(11).
  Botros, Miriam; Gonzalez‐Julian, Jesus; Scherer, Torsten; Popescu, Radian; Loho, Christoph; Kilmametov, Askar; Clemens, Oliver & Hahn, Horst
  
• One-Step Mechanochemical Synthesis of Nanostructured and Non-Equilibrium Complex Oxides. Encyclopedia of Green Chemistry, 473-482. Elsevier.
  Šepelák, Vladimír; Harničárová, Marta; Valíček, Jan & Becker, Klaus Dieter