First-Principles and Experimental Investigation of ABO4 Zircons as Calcium Intercalation Cathodes

Identifying next-generation batteries with multivalent ions, such as Ca2+ is an active area of research to meet the increasing demand for large-scale, renewable energy storage solutions. Despite the promise of higher energy densities with multivalent batteries, one of their main challenges is addres...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Chemistry of materials 2024-05, Vol.36 (9), p.4444-4455
Hauptverfasser: Kim, Jiyoon, Sari, Dogancan, Chen, Qian, Rutt, Ann, Ceder, Gerbrand, Persson, Kristin A.
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:Identifying next-generation batteries with multivalent ions, such as Ca2+ is an active area of research to meet the increasing demand for large-scale, renewable energy storage solutions. Despite the promise of higher energy densities with multivalent batteries, one of their main challenges is addressing the sluggish kinetics in cathodes that arise from stronger electrostatic interactions between the multivalent ion and host lattice. In this paper, zircons are theoretically and experimentally evaluated as Ca cathodes. A migration barrier as low as 113 meV is computationally found in YVO4, which is the lowest Ca2+ barrier reported to date. Low barriers are confirmed across 18 zircon compositions, which are related to the low coordination change and reduced interstitial site preference of Ca2+ along the diffusion pathway. Among the four materials (BiVO4, YVO4, EuCrO4, and YCrO4) that were synthesized, characterized, and electrochemically cycled, the highest initial capacity of 81 mA h/g and the most reversible capacity of 65 mA h/g were achieved in YVO4 and BiVO4, respectively. Despite the facile migration of multivalent ions in zircons, density functional theory predictions of the unstable, discharged structures at higher Ca2+ concentrations (Ca x>0.25ABO4), the low dimensionality of the migration pathway, and the defect analysis of the B site atom can rationalize the limited intercalation observed upon electrochemical cycling.
ISSN:0897-4756
1520-5002
DOI:10.1021/acs.chemmater.4c00062