Journal Article

PUBDB-2026-01153

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Lithiation mechanisms of Li$_3$V$_2$(PO$_4$)$_3$

Andersen, B. P. (First author)Extern* ; Johansen, M.Extern*DESY* ; Ravnsbæk, D. B. (Corresponding author)

2026
Elsevier New York, NY [u.a.]

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Please use a persistent id in citations: doi:10.1016/j.jpowsour.2026.239920  doi:10.3204/PUBDB-2026-01153

Abstract: Lithium vanadium phosphate, Li$_3$V$_2$(PO$_4$)$_3$, is widely explored in terms of the reversible extraction of three Li-ions above 3 V vs. Li. Yet, important aspects of the lithiation behavior of Li$_3$V$_2$(PO$_4$)$_3$ at low potentials remain unresolved. Reports suggest that deep lithiation leads to Li$_7$V$_2$(PO$_4$)$_3$ and even conversion to V(0) and Li$_3$PO$_4$, however, definitive structural evidence is lacking. Here, we investigate the phase evolution of Li-ion insertion in Li$_3$V$_2$(PO$_4$)$_3$ at low potential using a combination of synchrotron X-ray diffraction, scattering and spectroscopy, electrochemical analysis and void space modeling. We show that the monoclinic Li$_3$V$_2$(PO$_4$)$_3$ framework can accommodate up to two additional Li-ions, forming Li$_4$V$_2$(PO$_4$)$_3$ and Li$_5$V$_2$(PO$_4$)$_3$. Below 1.6 V the material undergoes a structural transition into a lithium vanadium phosphate phase with Li:V > 2.5, which differs from the parent Li$_3$V$_2$(PO$_4$)$_3$. At deep discharge, vanadium is reduced below an oxidation state of V(II), yet no crystalline V-metal or Li$_3$PO$_4$ is detected at any state of discharge, excluding a conventional conversion reaction at deep discharge. These findings detail the lithiation mechanism of Li$_3$V$_2$(PO$_4$)$_3$ and establish the true limits of Li storage in the anti-NASICON structure, with implications for its use as a high-capacity electrode and for the broader design of polyanionic hosts operating at low potentials.

Note: Proposal No.: H-20010169 (mail-in)Funding: Novo Nordisk Foundation (grant no. NNF20OC0062068), Danish National Research Foundation (grant no. DNRF189) through Center for Sustainable Energy Materials, CENSEMAT.

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)
2. PETRA-D (FS-PETRA-D)

Research Program(s):

1. 632 - Materials – Quantum, Complex and Functional Materials (POF4-632) (POF4-632)
2. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
3. FS-Proposal: I-20211012 (I-20211012) (I-20211012)
4. FS-Proposal: I-20230834 (I-20230834) (I-20230834)
5. STREAMLINE - Sustainable research at micro and nano X-ray beamlines (870313) (870313)

Experiment(s):

1. PETRA Beamline P02.1 (PETRA III)

Appears in the scientific report 2026

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