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  • Toward Stable, High‐Energy, Partially Disordered Mn‐Rich Spinel Cathodes by Revealing and Mitigating Surface Degradation
Title: Toward Stable, High‐Energy, Partially Disordered Mn‐Rich Spinel Cathodes by Revealing and Mitigating Surface Degradation
Abstract Mn‐rich cathodes balance performance and sustainability but suffer from limited cyclability due to Mn dissolution and cathode‐to‐anode crosstalk. The Jahn‐Teller (J‐T) effect of Mn3+is often linked to the above phenomena, such as in spinel LiMn2O4. However, in typical voltage ranges, significant Mn3+only appears near the end of discharge, highlighting the need to reassess its role in driving Mn dissolution, structural degradation, and battery performance. Here, the spinel cathode's degree of disorder is tailored to expand the Mn redox range, enabling segmentation into J‐T active and less active voltage ranges. Cycling at segmented voltage windows reveals surface degradation mechanisms with and without the major J‐T effect. Despite a stronger J‐T effect below 3.6 V vs. Li/Li+, Mn dissolution is less significant than above 3.6 V. Expanding the cycling window to 2.0–4.3 V causes severe degradation as the J‐T active range induces a tetragonal phase and Mn2+‐rich surface, driving Mn dissolution and consuming Li‐ion inventory in full cells. Reducing electrolyte acidity minimizes Mn3+disproportionation, enabling a stable dopant‐free Mn‐only cathode with a 250 mAh g−1specific capacity. These findings demonstrate that full cells using Mn‐rich cathodes have the potential to avoid the notorious crosstalk problem through electrolyte engineering.  more » « less
Award ID(s):
2615937 2045570
PAR ID:
10666425
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley
Date Published:
Journal Name:
Advanced Materials
Volume:
37
Issue:
34
ISSN:
0935-9648
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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