Unravelling Charge Carrier Mobility in d0‐Metal‐based Spinels. Issue 7 (1st June 2022)

• Record Type: Journal Article
• Authors: Dillenz, Manuel; Sotoudeh, Mohsen; Glaser, Clarissa; Janek, Jürgen; Groß, Axel; Euchner, Holger
• Is Part Of: Batteries & supercaps. Volume 5:Issue 7(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-06-01
• Subjects: descriptor -- ion mobility -- scaling relation -- solid electrolyte -- spinel; Electrochemistry -- Periodicals; Electrodes -- Periodicals; Electric batteries -- Periodicals; 621.31242
• DOI: 10.1002/batt.202200164
• Languages: English
• ISSNs: 2566-6223

Abstract

Abstract: Enabling high Mg ion mobility, spinel‐type materials are promising candidates for cathode or solid electrolyte applications. To elucidate the factors governing the observed high mobility of multivalent ions, periodic DFT calculations of various charge carriers (A=Li, Na, K, Mg, Ca, Zn and Al) in the ASc2 S4 and ASc2 Se4 spinel compounds were performed, resulting in the identification of a Brønsted‐Evans‐Polanyi‐type scaling relation for the migration barriers of the various charge carriers. Combining this scaling relation with the derivation of a descriptor, solely based on easily accessible observables, constitutes a conceptual framework to investigate ion mobility in d 0 ‐metal‐based spinel chalcogenides with significantly reduced computational effort. This approach was exemplarily verified for various d 0 ‐metal‐based spinel chalcogenide compounds AB2 X4 (B=Sc, Y, Ga, In, Er and Tm; X=O, S and Se) and led to the identification of d 0 ‐metal‐based CaB2 O4 spinels as promising compounds possibly enabling high Ca ion mobility. Abstract : Enabling high Mg ion mobility, spinel‐type materials are promising candidates for cathode or solid electrolyte applications in batteries. In this work, density functional theory based calculations were performed to elucidate the kinetics of different charge carriers (A=Li, Na, K, Mg, Ca, Zn and Al) in d 0 ‐metal‐based spinel chalcogenides. This resulted in the identification of a Brønsted‐Evans‐Polanyi‐type scaling relation for the migration barriers and a descriptor for the charge carrier site preference, solely based on easily accessible observables.