Defect-Induced Phenomena in Perovskites under Realistic External Conditions (DEFTD) Gauss Centre for Supercomputing e.V.


Defect-Induced Phenomena in Perovskites under Realistic External Conditions (DEFTD)

Principal Investigator:
Eugene A. Kotomin

Department of Physical Chemistry of Solids, Max-Planck Institute for Solid State Research, Stuttgart (Germany)

Local Project ID:

HPC Platform used:
Hazel Hen of HLRS

Date published:

Fuel cellsand batteries are expected to play very important roles in future energy supply. While ambient-temperature fuel cells transforming chemical energy into electricity suffer from sluggish kinetics, high temperature (>800 °C) fuel cells suffer from limited long-term stability. Fuel cells operating at 250-500°C with ceramic proton-conducting oxide electrolytes (H-SOFC) promise the desired compromise between cost, rapid start-up time and stability because H-SOFCs (i) can fast reach the operating temperature; (ii) do not require noble metals for electrodes; and (iii) do not have materials problems typical for high temperature cells.

Materials for the solid electrolyte, the heart of H-SOFC, and for anodes are relatively well established. However, finding an efficient cathode material still poses a problem because the cathode reaction becomes the rate limiting factor. In currently used cathode materials and composites, oxygen reduction is believed to be restricted to three-phase contacts, leading to insufficient current density. Finding a stable p-type conductor with sufficient proton conductivity would provide such efficient cathode materials and pave the way to large scale application of H-SOFC.

Our project is focused on massive parallel computer modeling of new prospective perovskite materials for the fuel cells from first principles. This requires calculations of the atomic, electronic, and magnetic properties without any a priori assumptions, so called ab initio or first principles. Understanding of a role of dopants and defects is a key to predict the improvement of device performance which is validated later on experimentally.

Typical materials are ABO3 type perovskites and solid solutions, e.g. (La,Sr)(Co,Fe)O3. Addressing realistic operational conditions is achieved via combination with ab initio thermodynamics. The accurate state of the art first principles calculations of large supercells with low symmetry are very time consuming and need use of supercomputing technologies as provided in particular by the High-Performance Computing Center Stuttgart (HLRS). We used primarily the CRAY XC40 system (Hazel Hen) with several thousand cores used in defect calculations. Primarily, the massive parallel computer codes VASP and CRYSTAL were employed.

In our theoretical modelling, we identified the rate determining step of the oxygen reduction reaction on cathode surfaces, the optimal cathode terminations, and reasons why oxygen transport is so efficient in BSCF material.

The planned insight into the proton uptake and proton migration process in ferrates and cobaltates could greatly promote development of more efficient cathode materials for intermediate-temperature fuel cells based on proton-conducting oxide electrolytes. Exploring new solid materials as fast ion conductor electrolytes to produce high performance all-solid-state batteries is an active field of research. In this project, using ab initio-based calculations, we investigate also the mechanism of ionic conductivity and superionic behavior in three promising solid electrolytes for batteries, namely Li2Sn2S5, LiSCN and NaSCN. All these materials are expected to behave as superionic conductors at elevated temperatures.

We use density functional theory (DFT) calculations for finding the ground state atomic and electronic structures, mechanisms and values of ionic conductivity and superionic phase transition temperature. We will then compare our theoretical results with the findings of our experimental collaborators in Max-Planck Institute for Solid State Research and provide atomistic insight into the transport properties in these materials which will be very helpful to shed light on experimental observations.

The results of our research were published in leading chemical and physical journals. 

Publications supported by DEFTD project (2013-2019) 

1. E. Heifets, E.A. Kotomin, A.A. Bagaturyants, J. Maier. Thermodynamic stability of non-stoichiometric SrFeO3-d: a hybrid DFT study. Phys. Chem. Chem. Phys., 21, 3918-3931 (2019). DOI: 10.1039/c8cp07117a

2.D. Fuks, D. Gryaznov, E.A. Kotomin, A. Chesnokov, and J. Maier. Dopant solubility in ceria: alloy thermodynamics combined with the DFT+U calculations. Solid State Ionics, 325, 258–264 (2018). DOI: 10.1016/j.ssi.2018.08.019

3. M.F. Hoedl, E. Makagon, I. Lubomirsky, R. Merkle, E.A. Kotomin, and J. Maier.
Impact of point defects on the elastic properties of BaZrO3: comprehensive insight from experiments and ab initio calculations. Acta Mater., 160, 247-256 (2018). DOI: 10.1016/j.actamat.2018.08.042

4. Yu.A. Mastrikov, R. Merkle, E.A. Kotomin, M.M. Kuklja, and J. Maier. Surface termination effects on the oxygen reduction reaction rate at fuel cell cathodes. J. Mater. Chem. A, 6, 11929–11940 (2018). DOI: 10.1039/c8ta02058b

5. A. Platonenko, D. Gryaznov, Yu. Zhukovskii,  E.A. Kotomin, Ab initio simulations of charged interstitial oxygen ions in corundum. —Nucl. Inst. Meth. B, 435, 74 (2018)

6.  E.A. Kotomin, R. Merkle, Yu. Mastrikov, M.M. Kuklja, J. Maier. The effects of (La,Sr)MnO3 cathode surface termination on ist electronic structure. — Trans. Electrochem.Soc. 77, 67 (2017) DOI: 10.1149/07710.0067ecst

7. E. Heifets, E.A. Kotomin, A. Bagaturyants, J. Maier. Thermodynamic stability of stoichiometric LaFeO3 and BiFeO3: a hybrid DFT study. — Phys Chem Chem Phys., 19, 3738 (2017)  DOI: 10.1039/c6cp07986e 

8. M. Arrigoni, E.A. Kotomin, J. Maier. First principles study of perovskite ultrathin films: stability and confinement effects. — Israel Journal of Chem., 57, 509 (2017). DOI:10.1002/ijch.201600056

9. R.A. Evarestov, D. Gryaznov, M. Arrigoni, E.A. Kotomin, A. Chesnokov, J. Maier. Use of site symmetry in supercell model of defective crystals: polarons in CeO2. — Phys Chem Chem Phys., 19, 8340 (2017). DOI: 10.1039/c6cp08582b

10. D. Gryaznov, R. Merkle, E.A. Kotomin, J. Maier. Ab initio modelling of oxygen vacancies and protonic defects in (La,Sr)FeO3 perovskite solutions. — J. Mater. Chem. A, 4, 13093 (2016)  DOI: 10.1039/c6ta04109d

11. M. Arrigoni, E.A. Kotomin, J. Maier.  Large-Scale Modeling of Defects in Advanced Oxides: Oxygen Vacancies in BaZrO3 Crystals.—Chapter in a book: "High Performance Computing in Science and Engineering '15" (Springer, Berlin, 2016) DOI 10.1007/978-3-319-24633-8_12

12.  M. Arrigoni, E. Kotomin, D. Gryaznov, and J. Maier.  Confinement effects for the F center in non-stoichiometric BaZrO3 ultrathin films.—Phys. Status Solidi B 252, 139–143 (2015).  DOI 10.1002/pssb.201400116

13. D. Gryaznov, S. Baumann, E. A. Kotomin, and R. Merkle.  Comparison of Permeation Measurements and Hybrid Density Functional Calculations on Oxygen Vacancy Transport in Complex Perovskite Oxides.—J. Phys. Chem. C, 118, 29542−29553 (2014). 

14F.U. Abuova, E.A. Kotomin , V.M. Lisitsyn, A.T. Akilbekov, S. Piskunov.Ab initio modeling of radiation damage in MgF2 crystals. — Nucl. Instr. and Meth. in Physics Research B 326, 314–317 (2014).

15.  A. B. Usseinov, E. A. Kotomin, A. T. Akilbekov, Yu. F. Zhukovskii, and J. Purans. Hydrogen adsorption on the ZnO (1100) surface: ab initio hybrid density functional linear combination of atomic orbitals calculations. — Physica Scripta, 89, 045801 (2014) doi:10.1088/0031-8949/89/04/045801

16. A.B. Usseinov, E.A. Kotomin, A.T. Akilbekov, Yu F. Zhukovskii, J. Purans. Hydrogen induced metallization of ZnO (1100) surface: Ab initio study. — Thin Solid Films,  553  38–42 (2014).

17. E. Blokhin, R. A. Evarestov, D. Gryaznov, E. A. Kotomin, and J. Maier.  Theoretical modeling of antiferrodistortive phase transition for SrTiO3 ultrathin films. — Phys. Rev. B 88, 241407(R) (2013). DOI: 10.1103/PhysRevB.88.241407


Institute of Solid State Physics, University of Latvia, Riga, Latvia

Scientific Contact:

Prof. Dr. Eugene A. Kotomin
Max Planck Institute for Solid State Research
Physical Chemistry of Solids (Joachim Maier)
Heisenbergstraße 1, D-70569 Stuttgart (Germany)
e-mail: E.Kotomin [@]
Physical Chemistry of Solids (Joachim Maier)


September 2019

Tags: HLRS Materials Science Max Planck Institute for Solid State