Electron paramagnetic resonance on impurity copper ions in sodium trititanate with a hierarchical two-level architecture

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Abstract

The results of studies of electron paramagnetic resonance on impurity copper ions in sodium trititanate (Na2Ti3O7) with a hierarchical two-level architecture, potentially suitable for use as negative electrodes of sodium-ion batteries, are presented. The main emphasis in the work was placed on the identification of magnetically different centers of the impurity copper ion, establishing the positions of these centers in the crystal lattice, determining the nature of their distributions in the volume of the sample, and elucidating the charge compensation mechanism for aliovalent substitutions. For Cu2+ ions in positions of Ti4+ substitution, the degree of a spin density delocalization from the bottom dx2-y2 orbital to the σ-orbitals of the nearest equatorial oxygen ions was estimated.

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Denis A. Saritsky

Institute of Chemistry FEB RAS

Email: denissaricki@mail.ru
ORCID iD: 0009-0006-2195-1042

Junior Researcher

Russian Federation, Vladivostok

Albert M. Ziatdinov

Institute of Chemistry FEB RAS

Author for correspondence.
Email: ziatdinov@ich.dvo.ru
ORCID iD: 0000-0001-7917-9207

Doctor of Sciences in Physics and Mathematics, Chief Researcher, Head of the Laboratory

Russian Federation, Vladivostok

Veniamin V. Zheleznov

Institute of Chemistry FEB RAS

Email: zhvv53@mail.ru

Doctor of Sciences in Chemistry, Leading Researcher

Russian Federation, Vladivostok

Denis P. Opra

Institute of Chemistry FEB RAS

Email: dp.opra@gmail.com
ORCID iD: 0000-0003-4337-5550

Candidate of Sciences in Chemistry, Senior Researcher, Head of the Laboratory

Russian Federation, Vladivostok

Sergey V. Gnedenkov

Institute of Chemistry FEB RAS

Email: svg21@hotmail.com
ORCID iD: 0000-0003-1576-8680

Corresponding Member of the RAS, Doctor of Sciences in Chemistry, Professor, Director

Russian Federation, Vladivostok

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2. Fig. 1. Contours of the first (d1) and second (d2) derivatives of microwave field energy absorption with respect to the external magnetic field by NTO-Cu-x powders (x = 35, 45, 60, 65, 100 and 130) at −160°C

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3. Fig. 2. Contours of the first (d1) and second (d2) derivatives of microwave field absorption with respect to the external magnetic field by NTO-Cu-35 powder at different temperatures

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4. Fig. 3. Experimental and theoretical contours of the first (d1) and second (d2) derivatives of microwave absorption with respect to the external magnetic field by NTO-Cu-35 powder at −160°C. The contours of the spectra of Cu2+ centers of types I and II were calculated using spin Hamiltonian 1 with the corresponding parameters from Table 1.

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5. Fig. 4. Experimental and theoretical contours of the first (d1) and second (d2) derivatives of microwave field absorption with respect to the external magnetic field by NTO-Cu-35 powder at −160°C. The contours of the spectra of Cu2+ centers of types I, II and III were calculated using spin Hamiltonian 1 with the corresponding parameters from Table 2.

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6. Fig. 5. Orbital energy levels and states of an ion with the d9 configuration in the crystal field of octahedral symmetry (Oh), as well as in the presence of tetragonal (D4h) and rhombic (D2h) distortions of this symmetry

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