Authors
Yan Liu, Xiao-Tong Wang, Heng Zhang, Jin-Ling Liu, Miao Du, Han-Hao Liu, Xin-Yi Zhang, Dai-Huo Liu, Zhen-Yi Gu, Xing-Long Wu
Published in
Journal of the American Chemical Society. Jul 05, 2026. Epub Jul 05, 2026.
Abstract
FeMn-based polyanionic phosphates, represented by Na4FeMn(PO4)3, are promising cathode materials for low-cost and sustainable sodium-ion batteries due to their high theoretical voltage and capacity. Nevertheless, their performance is constrained by long-standing and unexplained anomalous electrochemical inertness. This study unveils the physical origin of this inertness and identifies an intrinsic electronic "spatiotemporal confinement effect". Spatially, PO4 tetrahedra separate the redox-active MO6 (M = Fe/Mn) units into mutually isolated compartments; temporally, spin-pairing constraints further impede charge transport within the d-electron configuration. Based on this mechanism, we propose a heterometallic bridging strategy by introducing V and Ti with empty 3d-orbitals as electronic bridges to reconstruct electronic connectivity within the Fe-Mn network. The prepared Na3.6Fe0.6Mn0.6Ti0.5V0.3(PO4)3 successfully breaks the spatiotemporal confinement, circumvents spin-forbidden barriers, and activates multielectron redox reactions. Consequently, it achieves a leap from an inert state to high energy density of 470.1 Wh kg-1. Meanwhile, it exhibits exceptional wide-temperature adaptability, retaining 76.4 mAh g-1 at -80 °C and operating stably across 130 °C range. This work elucidates the nature of electrochemical inertness in FeMn-based polyanionic compounds through the lens of spatiotemporal confinement and provides a universal strategy for the design of high energy density polyanionic cathode materials.
PMID:
42402201
Bibliographic data and abstract were imported from PubMed on 06 Jul 2026.
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