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Title: Counter‐Intuitive Structural Instability Aroused by Transition Metal Migration in Polyanionic Sodium Ion Host
Abstract

The structure of polyanionic materials is conventionally known to be free of transition metal migration and structurally stable when storing/releasing sodium ions. Herein, the observation of enhanced cycling stability of a typical polyanionic cathode, Na3VCr(PO4)3(NVCP) at lower temperature (−15 °C vs 30 °C), triggers the exploration of its structural origins with a surprising finding that the migratable nature of vanadium in NVCP leads to detrimental structural degradation of the polyanionic host upon cycling. The correlation between long range and short range structural change associated with this atomic migration is established via a strong combination of various in situ/ex situ characterization tools, revealing the essential V–to–Na1 site migration. Such transition metal migration is effectively suppressed when V atoms are pinned to their original position in the lattice by lowering the temperature. More importantly and practically, a room temperature‐based deep sodiation strategy is further developed to recover the structure. This work challenges the long‐standing assumption of the stability of the polyanionic framework structure and calls for urgent attention to the structural understanding of the NVCP system as well as strategy development for property enhancement.

 
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Award ID(s):
1805938
NSF-PAR ID:
10454437
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Energy Materials
Volume:
11
Issue:
3
ISSN:
1614-6832
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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    Acknowledgment

    This work was partially supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 22011044) by KRISS.

    Figure 1

     

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