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

被引：0
作者：
Li, Feifan [1 ]
Li, Yaping [2 ]
Duffort, Victor [3 ]
Mentre, Olivier [3 ]
Minaud, Claire [3 ]
Huang, Qingqing [2 ]
Cheng, Xiedong [1 ]
Cui, Rui [4 ]
Lu, Minfeng [1 ]
机构：
[1] Jiangsu Univ Sci & Technol, Sch Mat Sci & Engn, Zhenjiang 212100, Jiangsu, Peoples R China
[2] Jiangsu Univ Sci & Technol, Sch Environm & Chem Engn, Zhenjiang 212003, Jiangsu, Peoples R China
[3] Univ Artois, Univ Lille, UMR 8181 UCCS Unite Catalyse & Chim Solide, CNRS,Cent Lille,ENSCL, F-59000 Lille, France
[4] Jiangsu Univ Sci & Technol, Sch Met & Mat Engn, Zhangjiagang 215600, Jiangsu, Peoples R China
来源：
DALTON TRANSACTIONS | 2025年 / 54卷 / 07期
基金：
中国国家自然科学基金;
关键词：
MAGNETIC-STRUCTURE; MN; FE; LI; DIFFRACTION; CALCIUM; CATHODE; CO;
D O I：
10.1039/d4dt03027c
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Three new sodium manganese fluoro-pyrophosphate compounds, namely, Na5.5Mn1.5(P2O7)2F0.5 (I), Na7Mn0.75(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 [Mn0.75(P2O7)2F2]7- unit, whereas I and III reveal three-dimensional (3D) frameworks that consist of MnO6, Mn/NaO5F0.5 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 degrees 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 similar to 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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页码：2974 / 2984
页数：11
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