Alleviating the stability-energy density dilemma via electron-donor-mediated orbital symmetry regulation in sodium phosphate cathodes
- 1MOE Key Laboratory for UV Light-Emitting Materials and Technology, Northeast Normal University, Changchun, Jilin 130024, P. R. China.
- 2Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, P. R. China.
Abstract
Manganese-based sodium super ionic conductor-type cathode materials, leveraging the multielectron redox activity of manganese, represent a promising pathway toward high-energy-density sodium-ion batteries (SIBs). However, the unavoidable generation of Mn³⁺(3d⁴) species during charge-discharge processes, characterized by asymmetric eg orbital occupancy, triggers octahedral symmetry breaking. This inherent electronic structural instability creates a fundamental contradiction between achieving high energy density and ensuring long cycle life that remains inherently difficult to reconcile. Here, we report an electron-donor-mediated (EDM) mechanism that suppresses Mn³⁺-induced octahedral distortion while preserving high-spin functionality. As electron-donating Fe³⁺ and V³⁺ are incorporated, Mn³⁺ 3d electrons undergo partial delocalization. This electronic redistribution promotes orbital interactions between neighboring transition metal sites through the transition metal-oxygen framework, driving the eg orbitals toward a more symmetric occupation and suppressing octahedral distortion. The EDM-modified cathode demonstrates a high energy density of 492.06 Wh kg⁻¹. It delivers 178.8 mAh g⁻¹ at 0.1 C and retains 80.2% of its capacity over 2000 cycles at 10 C, paving a novel pathway toward next-generation high-performance SIBs cathode materials.
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BibTeX
@article{zhang2026alleviating,
title = {{Alleviating the stability-energy density dilemma via electron-donor-mediated orbital symmetry regulation in sodium phosphate cathodes}},
author = {Heng Zhang and Zhen-Yi Gu and Xiao-Tong Wang and Yong-Li Heng and Yan Liu and Xin-Ru Zhang and Rong-Jie Zhe and Xing-Long Wu},
journal = {Science Advances},
year = {2026},
month = oct,
doi = {10.1126/sciadv.aeh8668},
url = {https://www.science.org/doi/abs/10.1126/sciadv.aeh8668},
note = {CC BY-NC},
}
RIS
TY - JOUR
TI - Alleviating the stability-energy density dilemma via electron-donor-mediated orbital symmetry regulation in sodium phosphate cathodes
AU - Heng Zhang
AU - Zhen-Yi Gu
AU - Xiao-Tong Wang
AU - Yong-Li Heng
AU - Yan Liu
AU - Xin-Ru Zhang
AU - Rong-Jie Zhe
AU - Xing-Long Wu
PY - 2026
DA - 2026/10/30
JO - Science Advances
DO - 10.1126/sciadv.aeh8668
UR - https://www.science.org/doi/abs/10.1126/sciadv.aeh8668
AB - Manganese-based sodium super ionic conductor-type cathode materials, leveraging the multielectron redox activity of manganese, represent a promising pathway toward high-energy-density sodium-ion batteries (SIBs). However, the unavoidable generation of Mn³⁺(3d⁴) species during charge-discharge processes, characterized by asymmetric eg orbital occupancy, triggers octahedral symmetry breaking. This inherent electronic structural instability creates a fundamental contradiction between achieving high energy density and ensuring long cycle life that remains inherently difficult to reconcile. Here, we report an electron-donor-mediated (EDM) mechanism that suppresses Mn³⁺-induced octahedral distortion while preserving high-spin functionality. As electron-donating Fe³⁺ and V³⁺ are incorporated, Mn³⁺ 3d electrons undergo partial delocalization. This electronic redistribution promotes orbital interactions between neighboring transition metal sites through the transition metal-oxygen framework, driving the eg orbitals toward a more symmetric occupation and suppressing octahedral distortion. The EDM-modified cathode demonstrates a high energy density of 492.06 Wh kg⁻¹. It delivers 178.8 mAh g⁻¹ at 0.1 C and retains 80.2% of its capacity over 2000 cycles at 10 C, paving a novel pathway toward next-generation high-performance SIBs cathode materials.
SN - 2375-2548
ER -