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Title: AMOEBA Force Field Trajectories Improve Predictions of Accurate p K a Values of the GFP Fluorophore: The Importance of Polarizability and Water Interactions
Award ID(s):
1714555
PAR ID:
10382876
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
The Journal of Physical Chemistry B
Volume:
126
Issue:
40
ISSN:
1520-6106
Page Range / eLocation ID:
7806 to 7817
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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