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Title: Experimental and Computational Study of the Lithiation of Ba 8 Al y Ge 46–y Based Type I Germanium Clathrates
Award ID(s):
1710017 1206795
PAR ID:
10097003
Author(s) / Creator(s):
; ; ; ; ;
Date Published:
Journal Name:
ACS Applied Materials & Interfaces
Volume:
10
Issue:
44
ISSN:
1944-8244
Page Range / eLocation ID:
37981 to 37993
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. Abstract

    Vanadium multiredox‐based NASICON‐NazV2−yMy(PO4)3(3 ≤z ≤ 4; M = Al3+, Cr3+, and Mn2+) cathodes are particularly attractive for Na‐ion battery applications due to their high Na insertion voltage (>3.5 V vs Na+/Na0), reversible storage capacity (≈150 mA h g−1), and rate performance. However, their practical application is hindered by rapid capacity fade due to bulk structural rearrangements at high potentials involving complex redox and local structural changes. To decouple these factors, a series of Mg2+‐substituted Na3+yV2−yMgy(PO4)3(0 ≤y ≤ 1) cathodes is studied for which the only redox‐active species is vanadium. While X‐ray diffraction (XRD) confirms the formation of solid solutions between they = 0 and 1 end members, X‐ray absorption spectroscopy and solid‐state nuclear magnetic resonance reveal a complex evolution of the local structure upon progressive Mg2+substitution for V3+. Concurrently, the intercalation voltage rises from 3.35 to 3.45 V, due to increasingly more ionic VO bonds, and the sodium (de)intercalation mechanism transitions from a two‐phase fory ≤ 0.5 to a solid solution process fory ≥ 0.5, as confirmed by in operando XRD, while Na‐ion diffusion kinetics follow a nonlinear trend across the compositional series.

     
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