Obtaining V2(PO4)3 by sodium extraction from single-phase NaxV2(PO4)3 (1 < x < 3) positive electrode materials

IF 37.2 1区材料科学 Q1 CHEMISTRY, PHYSICAL Nature Materials Pub Date : 2024-10-23 DOI:10.1038/s41563-024-02023-7

Sunkyu Park, Ziliang Wang, Kriti Choudhary, Jean-Noël Chotard, Dany Carlier, François Fauth, Pieremanuele Canepa, Laurence Croguennec, Christian Masquelier

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Abstract

We report on single-phase Na_xV₂(PO₄)₃ compositions (1.5 ≤ x ≤ 2.5) of the Na super ionic conductor type, obtained from a straightforward synthesis route. Typically, chemically prepared c-Na₂V₂(PO₄)₃, obtained by annealing an equimolar mixture of Na₃V₂(PO₄)₃ and NaV₂(PO₄)₃, exhibits a specific sodium-ion distribution (occupancy of the Na(1) site of only 0.66(4)), whereas that of the electrochemically obtained e-Na₂V₂(PO₄)₃ (from Na₃V₂(PO₄)₃) is close to 1. Unlike conventional Na₃V₂(PO₄)₃, when used as positive electrode materials in Na-ion batteries, the Na_xV₂(PO₄)₃ compositions lead to unusual single-phase Na⁺ extraction/insertion mechanisms with continuous voltage changes upon Na⁺ extraction/insertion. We demonstrate that the average equilibrium operating voltage observed upon Na⁺ deintercalation from single-phase Na₂V₂(PO₄)₃ is increased up to an average value of ~3.70 V versus Na⁺/Na (thanks to the activation of the V⁴⁺/V⁵⁺ redox couple) compared to 3.37 V versus Na⁺/Na in conventional Na₃V₂(PO₄)₃, thus leading to an increase in the theoretical energy density from 396.3 Wh kg^–1 to 458.1 Wh kg^–1. Electrochemical and chemical Na⁺ deintercalation from c-Na₂V₂(PO₄)₃ enables complete Na-ion extraction, increasing energy density.

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从单相 NaxV2(PO4)3 (1 < x < 3) 正极材料中通过钠萃取获得 V2(PO4)3

我们报告了通过直接合成路线获得的 Na 超级离子导体类型的单相 NaxV2(PO4)3 成分（1.5 ≤ x ≤ 2.5）。通常情况下，通过对 Na3V2(PO4)3 和 NaV2(PO4)3 的等摩尔混合物进行退火处理而化学制备的 c-Na2V2(PO4)3 显示出特定的钠离子分布（Na(1) 位点的占有率仅为 0.66(4)），而电化学制备的 e-Na2V2(PO4)3（来自 Na3V2(PO4)3）则接近 1。与传统的 Na3V2(PO4)3 不同，NaxV2(PO4)3 成分在用作瑙离子电池的正极材料时，会产生不同寻常的单相 Na+ 抽取/插入机制，并且在 Na+ 抽取/插入时会产生连续的电压变化。我们证明，从单相 Na2V2(PO4)3 中脱出 Na+ 时观察到的平均平衡工作电压与 Na+/Na 相比提高到 ~3.70 V（得益于 V4+/V5+ 氧化还原偶的激活），而传统 Na3V2(PO4)3 中与 Na+/Na 相比为 3.37 V，因此理论能量密度从 396.3 Wh kg-1 提高到 458.1 Wh kg-1。c-Na2V2(PO4)3 中 Na+ 的电化学和化学脱闰使 Na 离子完全提取出来，从而提高了能量密度。

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来源期刊

Nature Materials 工程技术-材料科学：综合

CiteScore

62.20

自引率

0.70%

发文量

221

审稿时长

3.2 months

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