Determination of oxygen vacancy limit in Mn substituted YSZ ceramics

TL;DR

This study investigates the maximum number of oxygen vacancies that can be introduced into Mn-doped YSZ ceramics, revealing a limit of 0.19 vacancies per formula unit through spectroscopic and magnetic analyses.

Contribution

It provides the first systematic determination of the oxygen vacancy limit in Mn-doped YSZ ceramics using advanced spectroscopic and magnetic techniques.

Findings

Oxygen vacancy limit is 0.19 per formula unit.

Mn oxidation states and local environments evolve with doping.

Mn3O4 precipitates form at x ≥ 0.1.

Abstract

The series of Mnx(Y0.148Zr0.852)1-xO2-{\delta} ceramics was systematically studied by means of X-ray absorption and emission spectroscopy and DC magnetic susceptibility. XAS and XES results show changes in manganese oxidation state and a gradual evolution of the local atomic environment around Mn ions upon increasing dopants content, which is due to structural relaxation caused by growing amount of oxygen vacancies. Magnetic susceptibility measurements reveal that Mn3O4 precipitates are formed for x greater than or equal to 0.1 and enable independent determination of actual quantity of Mn ions dissolved in YSZ solid solution. We show that amount of oxygen vacancies generated by manganese doping into YSZ is limited to 0.19 per formula unit.