Breaking the Electronic Conductivity Bottleneck of Manganese Oxide Family for High-Power Fluorinated Graphite Composite Cathode by Ligand-Field High-Dimensional Constraining Strategy
© 2022 Wiley-VCH GmbH.
| Veröffentlicht in: | Advanced materials (Deerfield Beach, Fla.). - 1998. - 35(2023), 8 vom: 09. Feb., Seite e2209210 |
|---|---|
| 1. Verfasser: | |
| Weitere Verfasser: | , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2023
|
| Zugriff auf das übergeordnete Werk: | Advanced materials (Deerfield Beach, Fla.) |
| Schlagworte: | Journal Article electronic conductivities fluorinated graphite high-dimensional constraining ligand-field stacking topology transition metal oxides |
| Zusammenfassung: | © 2022 Wiley-VCH GmbH. Primary lithium fluorinated graphite (Li/CFx ) batteries with superior energy density are an indispensable energy supply for multiple fields but suffer from sluggish reaction kinetics of the CFx cathode. Designing composite cathodes emerges as a solution to this problem. Despite the optimal composite component for CFx , the manganese oxide family represented by MnO2 is still faced with an intrinsic electronic conductivity bottleneck, which severely limits the power density of the composite cathode. Here, a cation-induced high-dimensional constraining strategy from the perspective of ligand-field stacking structure topological design, which breaks the molecular orbital hybridization of pristine semiconductive oxides to transform them into the high-conductivity metallic state while competitively maintaining structural stability, is proposed. Through first-principles phase diagram calculations, mixed-valent Mn5 O8 ( Mn 2 2 + Mn 3 4 + O 8 ${\rm{Mn}}_2^{2 + }{\rm{Mn}}_3^{4 + }{{\rm{O}}_8}$ ) is explored as an ideal high-dimensional constraining material with satisfied conductivity and large-scale production feasibility. Experiments demonstrate that the as-proposed CFx Mn5 O8 composite cathode achieves 2.36 times the power density (11399 W kg-1 ) of pristine CFx and a higher CFx conversion ratio (86%). Such a high-dimensional field-constraining strategy is rooted in the established four-quadrant electronic structure tuning framework, which fundamentally changes the orbital symmetry under the ligand field to overcome the common conductivity challenge of wide transition metal oxide materials |
|---|---|
| Beschreibung: | Date Completed 24.02.2023 Date Revised 24.02.2023 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1521-4095 |
| DOI: | 10.1002/adma.202209210 |