Journal Article

PUBDB-2022-00537

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Elucidating the Impact of Mg Substitution on the Properties of NASICON‐Na$_{3+y}$V$_{ 2−y}$Mg$_y$(PO$_4$)$_ 3$ Cathodes

Ghosh, S.Extern* ; Barman, N.Extern* ; Gonzalez-Correa, E. ; Mazumder, M. ; Zaveri, A. ; Giovine, R. ; Manche, A. ; Pati, S. K. ; Clément, R. J. ; Senguttuvan, P. (Corresponding author)Extern*

2021
Wiley-VCH Weinheim

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Please use a persistent id in citations: doi:10.1002/adfm.202105463  doi:10.3204/PUBDB-2022-00537

Abstract: Vanadium multiredox-based NASICON-NazV2−yMy(PO$_4$)$_3$ (3 ≤ z ≤ 4; M = Al$^{3+}$, Cr$^{3+}$, and Mn$^{2+}$) cathodes are particularly attractive for Na-ion battery applications due to their high Na insertion voltage (>3.5 V vs Na$^+$/Na$^0$), 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 Mg$^{2+}$-substituted Na$_{3+y}$V$_{ 2−y}$Mg$_y$(PO$_4$)$_ 3$ (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 the y = 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 Mg$^{2+}$ substitution for V$^{3+}$. Concurrently, the intercalation voltage rises from 3.35 to 3.45 V, due to increasingly more ionic VO bonds, and the sodium (de)intercalation mechanism transitions from a two-phase for y ≤ 0.5 to a solid solution process for y ≥ 0.5, as confirmed by in operando XRD, while Na-ion diffusion kinetics follow a nonlinear trend across the compositional series.

Note: The authors acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III and the authors thank Dr. Edmund Welter for his assistance in using Beamline P65, and DST for financial assistance for the measurement at DESY.

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)

Research Program(s):

1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
2. INDIA-DESY - INDIA-DESY Collaboration (2020_Join2-INDIA-DESY) (2020_Join2-INDIA-DESY)

Experiment(s):

1. PETRA Beamline P65 (PETRA III)

Appears in the scientific report 2021

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Database coverage:
; ; Clarivate Analytics Master Journal List ; Current Contents - Electronics and Telecommunications Collection ; Current Contents - Engineering, Computing and Technology ; Current Contents - Physical, Chemical and Earth Sciences ; DEAL Wiley ; Ebsco Academic Search ; Essential Science Indicators ; IF >= 15 ; JCR ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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