β-NaVOPO4 obtained by a low-temperature synthesis process: A new 3.3 V cathode for sodium-ion batteries

He, Guang; Huq, Ashfia; Manthiram, Arumugam; Kan, Wang Hay

doi:10.1021/acs.chemmater.5b04992

Title: β-NaVOPO₄ obtained by a low-temperature synthesis process: A new 3.3 V cathode for sodium-ion batteries

Journal Article · Tue Feb 02 00:00:00 EST 2016 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.5b04992· OSTI ID:1261529

He, Guang ^[1]; Huq, Ashfia ^[2]; Manthiram, Arumugam ^[1]; Kan, Wang Hay ^[1]

Univ. of Texas, Austin, TX (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Vanadyl phosphates (VOPO₄) represent a class of attractive cathodes in lithium-ion batteries. However, the exploration of this type of materials in sodium-ion batteries is rare. Here, we report for the first time the synthesis of orthorhombic β-NaVOPO₄ by first chemically extracting lithium from beta-LiVOPO₄ and then inserting sodium into the obtained β-VOPO₄ by a microwave-assisted solvothermal process with NaI, which serves both as a reducing agent and sodium source. Intermediate Na_xVOPO₄ compositions with x = 0.3, 0.5, and 0.8 have also been obtained by controlling the amount of NaI in the reaction mixture. Joint Rietveld refinement of synchrotron X-ray diffraction (XRD) and neutron diffraction confirms that the fully sodiated β-NaVOPO₄ is isostructural with the lithium counterpart β-LiVOPO₄. Bond valence sum maps suggest that sodium ions possibly diffuse along the [010] direction in the lattice, similar to the ionic conduction pathway in β-LiVOPO₄. Although the initial discharge capacity is low due to the protons in the structure, it steadily increases with cycling with a long plateau at 3.3 V. As a result, ex situ XRD data of cycled β-VOPO₄ and β-NaVOPO₄ electrodes confirm the reversible reaction in sodium cells involving the V⁴⁺/V⁵⁺ redox couple.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1261529

Journal Information:: Chemistry of Materials, Vol. 28, Issue 5; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 52 works

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