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Ionic transport in K2Ti6O13

  • Olha Skurikhina ORCID logo EMAIL logo , Maria Gombotz ORCID logo , Mamoru Senna ORCID logo , Martin Fabián ORCID logo , Matej Baláž ORCID logo , Klebson Lucenildo Da Silva ORCID logo , Marcela Achimovičová ORCID logo , H. Martin R. Wilkening ORCID logo and Bernhard Gadermaier ORCID logo EMAIL logo
Published/Copyright: February 14, 2022
Zeitschrift für Physikalische Chemie
From the journal Zeitschrift für Physikalische Chemie Volume 236 Issue 6-8

Abstract

The increasing demand for batteries forced the development of energy storage systems that rely on materials consisting of abundant elements in the Earth’s crust. Switching from Li+ to K+ as the main ionic charge carrier needs highly conducting potassium-bearing electrolytes to realize K+ ion batteries (PIBs). The knowledge gained from the design of Li-ion batteries (LIBs) and Na-ion batteries (NIBs) may conceptually inspire also the establishment of PIBs. Considering, for instance, the hexatitanates Na2Ti6O13, Li2Ti6O13, and H2Ti6O13, which were previously investigated as components for LIBs and NIBs, here we investigated ion dynamics in the K-analog K2Ti6O13. Ionic transport in polycrystalline samples of K2Ti6O13 was studied in a moisture-free atmosphere by broadband impedance spectroscopy in a temperature range from 20 °C to 450 °C. The current study aims at establishing a correlation between structural features of K2Ti6O13 and long-range ionic transport. As expected for K+ transport in K2Ti6O13 with its geometrically obstructed structure, the overall activation energy of ion transport in the ternary oxide takes a rather high value of 0.97(2) eV. Almost the same result (0.95(3) eV) is obtained for the migration activation energy, which we extracted from the analysis of crossover frequencies of the corresponding conductivity isotherms. By comparing our results with those of Na2Ti6O13 (0.82 eV), Li2Ti6O13 (0.65 eV), and H2Ti6O13, we clearly see how the size of the mobile cation correlates with both specific conductivities and activation energies. This comparison points to K+ being the main charge carrier in K2Ti6O13. It also helps in laying the foundations to derive the relevant structure-property relationships in this class of materials.

Keywords: channel structure; conductivity; ionic transport; potassium hexatitanate; titanates
Corresponding authors: Olha Skurikhina, Institute of Geotechnics, Slovak Academy of Sciences, Košice, Slovakia; and Faculty of Materials, Metallurgy and Recycling, Technical University of Košice, Košice, Slovakia, E-mail: ; and Bernhard Gadermaier, Institute of Chemistry and Technology of Materials, Graz University of Technology, Graz, Austria, E-mail:
Dedicated to Paul Heitjans on the occasion of his 75th birthday.

Funding source: Vedecká grantová agentúra Ministerstva školstva, vedy, výskumu a športu Slovenskej republiky a Slovenskej akadémie vied

Award Identifier / Grant number: 2/0103/20

Funding source: Slovak Research and Development Agency

Award Identifier / Grant number: APVV-19-0526

Funding source: European Commission

Award Identifier / Grant number: 2020-1-SK01-KA103-077857

Funding source: DFG

Award Identifier / Grant number: WI3600

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This research was funded by Vedecká grantová agentúra Ministerstva školstva, vedy, výskumu a športu Slovenskej republiky a Slovenskej akadémie vied VEGA Grant No. 2/0103/20 as well as by the Slovak Research and Development Agency (project APVV-19-0526). The research was carried out due to the O.S.’s participation in the Erasmus+ program within project no. 2020-1-SK01-KA103-077857 implemented at the Technical University in Košice and financed from the resources of the European Commission and finished in the framework of Action Austria-Slovakia “Ernst-Mach Grant for PhD students”. Financial support by the DFG (WI3600) is also acknowledged.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2021-11-24
Accepted: 2022-01-27
Published Online: 2022-02-14
Published in Print: 2022-06-27

© 2022 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Preface
  3. Special issue on the occasion of the 75th birthday of Paul Heitjans
  4. Contribution to Special Issue dedicated to Paul Heitjans
  5. Unusual cation coordination in nanostructured mullites
  6. 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
  7. Two new quaternary copper bismuth sulfide halides: CuBi2S3Cl and CuBi2S3Br as candidates for copper ion conductivity
  8. Sintering behavior and ionic conductivity of Li1.5Al0.5Ti1.5(PO4)3 synthesized with different precursors
  9. Status and progress of ion-implanted βNMR at TRIUMF
  10. How Li diffusion in spinel Li[Ni1/2Mn3/2]O4 is seen with μ ±SR
  11. Nuclear magnetic resonance (NMR) studies of sintering effects on the lithium ion dynamics in Li1.5Al0.5Ti1.5(PO4)3
  12. Anion reorientations and cation diffusion in a carbon-substituted sodium nido-borate Na-7,9-C2B9H12: 1H and 23Na NMR studies
  13. Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: I. A multinuclear solid state NMR study of the system Li6PS5-xSexI and of Li6AsS5I
  14. Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: II. Multinuclear solid state NMR of the systems Li6PS5−x Se x Cl and Li6PS5−x Se x Br
  15. Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T 1 3D 7Li NMR of superionic Li10GeP2S12
  16. How the cation size impacts on the relaxational and diffusional dynamics of supercooled butylammonium-based ionic liquids: DPEBA–TFSI versus BTMA–TFSI
  17. Solid-state NMR studies of non-ionic surfactants confined in mesoporous silica
  18. Inorganic-organic hybrid materials based on the intercalation of radical cations: 2-(4-N-methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-N-oxide in fluoromica clay
  19. Lithium tracer diffusion in near stoichiometric LiNi0.5Mn1.5O4 cathode material for lithium-ion batteries
  20. On the CaF2-BaF2 interface
  21. The ionic conductivity of alkali aluminum germanium phosphate glasses – comparison of Plasma CAIT with two electrode DC measurements
  22. Thin-film chemical expansion of ceria based solid solutions: laser vibrometry study
  23. Predicting conductivities of alkali borophosphate glasses based on site energy distributions derived from network former unit concentrations
  24. Ionic transport in K2Ti6O13
  25. F anion transport in nanocrystalline SmF3 and in mechanosynthesized, vacancy-rich Sm1—x BaxF3—x
  26. An overview of thermotransport in fluorite-related ionic oxides
https://doi.org/10.1515/zpch-2021-3166
Keywords for this article
channel structure; conductivity; ionic transport; potassium hexatitanate; titanates

Articles in the same Issue

  1. Frontmatter
  2. Preface
  3. Special issue on the occasion of the 75th birthday of Paul Heitjans
  4. Contribution to Special Issue dedicated to Paul Heitjans
  5. Unusual cation coordination in nanostructured mullites
  6. 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
  7. Two new quaternary copper bismuth sulfide halides: CuBi2S3Cl and CuBi2S3Br as candidates for copper ion conductivity
  8. Sintering behavior and ionic conductivity of Li1.5Al0.5Ti1.5(PO4)3 synthesized with different precursors
  9. Status and progress of ion-implanted βNMR at TRIUMF
  10. How Li diffusion in spinel Li[Ni1/2Mn3/2]O4 is seen with μ ±SR
  11. Nuclear magnetic resonance (NMR) studies of sintering effects on the lithium ion dynamics in Li1.5Al0.5Ti1.5(PO4)3
  12. Anion reorientations and cation diffusion in a carbon-substituted sodium nido-borate Na-7,9-C2B9H12: 1H and 23Na NMR studies
  13. Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: I. A multinuclear solid state NMR study of the system Li6PS5-xSexI and of Li6AsS5I
  14. Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: II. Multinuclear solid state NMR of the systems Li6PS5−x Se x Cl and Li6PS5−x Se x Br
  15. Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T 1 3D 7Li NMR of superionic Li10GeP2S12
  16. How the cation size impacts on the relaxational and diffusional dynamics of supercooled butylammonium-based ionic liquids: DPEBA–TFSI versus BTMA–TFSI
  17. Solid-state NMR studies of non-ionic surfactants confined in mesoporous silica
  18. Inorganic-organic hybrid materials based on the intercalation of radical cations: 2-(4-N-methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-N-oxide in fluoromica clay
  19. Lithium tracer diffusion in near stoichiometric LiNi0.5Mn1.5O4 cathode material for lithium-ion batteries
  20. On the CaF2-BaF2 interface
  21. The ionic conductivity of alkali aluminum germanium phosphate glasses – comparison of Plasma CAIT with two electrode DC measurements
  22. Thin-film chemical expansion of ceria based solid solutions: laser vibrometry study
  23. Predicting conductivities of alkali borophosphate glasses based on site energy distributions derived from network former unit concentrations
  24. Ionic transport in K2Ti6O13
  25. F anion transport in nanocrystalline SmF3 and in mechanosynthesized, vacancy-rich Sm1—x BaxF3—x
  26. An overview of thermotransport in fluorite-related ionic oxides
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