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IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-01-14 DOI:10.1039/d4dt03027c

Feifan Li, Yaping Li, Victor Duffort, Olivier Mentré, Claire Minaud, Qingqing Huang, Xiedong Cheng, Rui Cui, Minfeng Lü

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引用次数: 0

摘要

通过在 NaNO3 和 KNO3 通量下加热 NaPF6、Na2PO3F 或 NaH2PO4 与不同锰源的混合物，合成了三种新的氟焦磷酸钠锰化合物，即 Na5.5Mn1.5(P2O7)2F0.5 (I)、Na7Mn0.75(P2O7)2F2 (II) 和 Na9Mn3(P2O7)4F (III)。通过单晶 X 射线衍射 (XRD) 对标题化合物的结构进行了表征。其中，Ⅰ和Ⅲ揭示了由 MnO6、Mn/NaO5F0.5 八面体或 MnO6 八面体以及带有 P2O7 单元的变形 MnO5 正方体金字塔组成的三维（3D）框架，Na+阳离子位于不同元环的一维（1D）隧道中。与高性能钠离子导体的活化能 0.4 eV 相比，III 的活化能更高，为 0.89 eV。对 Na+ 扩散路径的分析表明，通过键价能谱方法，渗流是通过沿 b 轴的之字形链发生的。此外，还报告了详细的特性分析，如光谱和磁性能以及 III 的比热。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Open frameworks in the NaxMny(P2O7)mFn fluoro-pyrophosphates system

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Open frameworks in the NaxMny(P2O7)mFn fluoro-pyrophosphates system

Three new sodium manganese fluoro-pyrophosphate compounds, namely, Na_5.5Mn_1.5(P₂O₇)₂F_0.5 (I), Na₇Mn_0.75(P₂O₇)₂F₂ (II), and Na₉Mn₃(P₂O₇)₄F (III), have been synthesized by heating a mixture of NaPF₆, Na₂PO₃F or NaH₂PO₄ with different Mn sources in NaNO₃ and KNO₃ fluxes. The structures of the title compounds were characterized via single-crystal X-ray diffraction (XRD). II is characteristic of a shell of Na⁺ ions that encloses one [Mn_0.75(P₂O₇)₂F₂]⁷⁻ unit, whereas I and III reveal three-dimensional (3D) frameworks that consist of MnO₆, Mn/NaO₅F_0.5 octahedra or MnO₆ octahedra and distorted MnO₅ square pyramids with P₂O₇ units, where Na⁺ cations reside in different-membered ring one-dimensional (1D) tunnels. The estimated total Na⁺ ion conductivity for a pellet of III in open air is 10⁻⁵ S cm⁻¹ at 400 °C, which is lower than that of many NASICON-type compounds at room temperature, with a higher activation energy of 0.89 eV for III compared to the value of ∼0.4 eV for high-performance sodium ion conductors. The analysis of Na⁺ diffusion pathways revealed that percolation occurs through a zig-zag chain along the b axis via the bond valence energy landscape approach. Detailed characterization, such as spectroscopic and magnetic properties and specific heat for III, is also reported.

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.