Batteries — Cathodes

Vanadium Phosphate Cathodes

NASICON- and tavorite-structured vanadium phosphates such as Na3V2(PO4)3 and LiVPO4F, combining high operating voltage with exceptional rate capability for both lithium- and sodium-ion systems.

At a glance

Class Statistics

Compounds Tracked
195
Multi-Source DFT
12
With Synthesis Routes
0
Avg. Agreement
0.00 / 1.00
Overview

What are Vanadium Phosphate Cathodes?

Vanadium phosphate cathodes represent a sophisticated class of polyanionic electrode materials that have garnered significant attention for their robust structural stability and high electrochemical performance in both lithium-ion and sodium-ion battery systems. These materials typically crystallize in NASICON or tavorite frameworks, which are characterized by three-dimensional open-channel structures that facilitate the rapid migration of alkali metal ions. The chemistry of these cathodes relies on the inductive effect of the phosphate polyanions, which effectively stabilizes the vanadium redox centers, allowing for high operating voltages and long-term structural integrity during repeated cycling. By utilizing the strong covalent bonding within the (PO4)3- units, these materials mitigate the degradation pathways often seen in traditional layered transition metal oxides. Notable members of this class include Na3V2(PO4)3, which is widely studied for its excellent power density and cycle life in sodium-ion batteries, and LiVPO4F, which leverages the high electronegativity of fluorine to push the operating potential to higher levels. The importance of vanadium phosphate cathodes lies in their ability to bridge the gap between high-energy density and high-power capability, making them ideal candidates for grid-scale energy storage and electric vehicle applications. Their inherent thermal stability also provides a significant safety advantage, as the strong P-O bonds prevent oxygen release at elevated temperatures. As research continues, the optimization of these materials through nanostructuring and carbon coating is further enhancing their electronic conductivity, solidifying their role as a cornerstone of next-generation battery technology.

Members

Top Vanadium Phosphate Cathodes

Ranked by data richness — literature synthesis coverage, multi-source DFT corroboration, and patent activity.

FormulaBand GapBest EAH (eV/atom)StabilityDFT SourcesRecipes
LiVPO40.65–3.04 eV0.0000On hull (stable)20
LiVPO51.04–3.16 eV0.0000On hull (stable)20
LiVP2O70.07–2.63 eV0.0000On hull (stable)20
LiVP3HO102.10–2.76 eV0.0365Metastable20
Li2O14P4V20.07–2.63 eV0.0000On hull (stable)20
Li4O20P4V41.04–3.16 eV0.0000On hull (stable)20
LiVP2HO81.25–1.54 eV0.0447Metastable20
Li12O58P16V60.02–1.61 eV0.0182Near hull (likely stable)10
Li5O29P8V30.02–1.34 eV0.0320Metastable10
Li2VPHO52.62–2.83 eV0.0638Metastable20
LiV2PO71.54 eV0.0906Metastable20
LiO7P2V0.07–2.63 eV0.0000On hull (stable)10
Li4O16P4V40.65–3.04 eV0.0000On hull (stable)10
Li8O40P8V81.04–3.16 eV0.0000On hull (stable)10
LiO4PV0.65–3.04 eV0.0000On hull (stable)10
NaVPO51.27–2.52 eV0.0000On hull (stable)10
Li2VP2O70.26–3.14 eV0.0167Near hull (likely stable)10
Na3VP2O90.43–1.13 eV0.0330Metastable10
Na4O20P4V41.27–2.52 eV0.0000On hull (stable)10
C2Na4O14P2V22.15 eV0.0000On hull (stable)10
Na2VPCO72.15 eV0.0000On hull (stable)10
H2Li2O16P4V21.25–1.54 eV0.0447Metastable10
Li3VPCO70.57–3.06 eV0.0686Metastable10
Li4O14P4V20.26–3.14 eV0.0167Near hull (likely stable)10
Li2O4PV1.26–2.97 eV0.0285Metastable10
Li18O58P16V60.02–2.08 eV0.0002On hull (stable)10
Li9O29P8V30.02–2.08 eV0.0002On hull (stable)10
HLiO10P3V2.10–2.76 eV0.0365Metastable10
Li4VP2O91.26–3.50 eV0.0721Metastable10
C4Na12O28P4V41.02–2.52 eV0.0124Near hull (likely stable)10
Li2VP3O102.14–2.22 eV0.0517Metastable10
Li8O20P4V41.13–1.54 eV0.0763Metastable10
B2Na4O14P2V20.29–1.52 eV0.0904Metastable10
F2Li2O8P2V21.62–1.97 eV0.0000On hull (stable)10
Li16O36P8V41.26–3.50 eV0.0721Metastable10
Li4O36P8V81.54 eV0.0107Near hull (likely stable)10
Li4V2P4H3O160.60 eV0.0269Metastable10
Li6O36P10V41.10 eV0.0758Metastable10
LiV2P2HO91.16 eV0.0700Metastable10
LiV2P3O102.70 eV0.0289Metastable10
LiV3P5O191.07 eV0.0791Metastable10
LiVPHO51.80–2.20 eV0.0000On hull (stable)10
LiVPO4F1.62–1.97 eV0.0000On hull (stable)10
Na2VBPO70.29–1.52 eV0.0904Metastable10
Na3VPCO71.02–2.52 eV0.0124Near hull (likely stable)10
H3Li4O16P4V20.60 eV0.0269Metastable10
H8Li4O38P8V61.79 eV0.0651Metastable10
Li2VP2HO82.13–2.39 eV0.0010On hull (stable)10
NaVPCO71.51–1.94 eV0.0367Metastable10
B2H6Na2O20P4V20.33 eV0.0005On hull (stable)10
Reference

Frequently Asked Questions

How many vanadium phosphate cathodes are in the database?

195 vanadium phosphate cathodes are tracked, of which 12 have multi-source DFT validation and 0 have documented synthesis routes.

More questions
What is the most data-rich vanadium phosphate cathode?
LiVPO4 is the most thoroughly characterized, with 50 reported structures.
Which vanadium phosphate cathode has the widest band gap?
Among the top compounds, Li4VP2O9 has the widest reported DFT band gap (3.50 eV).
Why are vanadium phosphate cathodes considered safer than traditional oxide cathodes?
The strong covalent bonding within the phosphate polyanion framework makes these materials thermally stable, preventing oxygen release and structural collapse during high-temperature operation.
What is the role of the NASICON structure in these materials?
The NASICON structure provides a three-dimensional open-channel framework that allows for the rapid diffusion of alkali metal ions, which is essential for achieving high power density.
Can vanadium phosphate cathodes be used for both lithium and sodium batteries?
Yes, their versatile structural frameworks are highly adaptable, allowing for efficient ion insertion and extraction in both lithium-ion and sodium-ion electrochemical systems.
How does the inductive effect influence the performance of these cathodes?
The inductive effect of the phosphate groups modifies the electronic environment of the vanadium centers, which helps to tune the redox potential and stabilize the crystal lattice during charge and discharge cycles.
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