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.
引用
收藏
页码：2974 / 2984
页数：11
相关论文
共 50 条
[21]   Preparation and electrochemical performance of nanowire-shaped Na3Mn2-xFex(P2O7)(PO4) for sodium-ion and lithium-ion batteries [J].
Chen, Yihao ;
Fan, Qinghua ;
Li, Jiajie ;
Chen, Ming ;
Jin, Haolin ;
Wen, Ni ;
Dong, Youzhong ;
Kuang, Quan ;
Zhao, Yanming .
DALTON TRANSACTIONS, 2022, 51 (10) :4173-4181
[22]   Understanding the Electrochemical Mechanism of the New Iron-Based Mixed-Phosphate Na4Fe3(PO4)2(P2O7) in a Na Rechargeable Battery [J].
Kim, Hyungsub ;
Park, Inchul ;
Lee, Seongsu ;
Kim, Hyunchul ;
Park, Kyu-Young ;
Park, Young-Uk ;
Kim, Haegyeom ;
Kim, Jongsoon ;
Lim, Hee-Dae ;
Yoon, Won-Sub ;
Kang, Kisuk .
CHEMISTRY OF MATERIALS, 2013, 25 (18) :3614-3622
[23]   Development of K4Fe3(PO4)2(P2O7) as a novel Fe-based cathode with high energy densities and excellent cyclability in rechargeable potassium batteries [J].
Park, Hyunyoung ;
Kim, Hyungsub ;
Ko, Wonseok ;
Jo, Jae Hyeon ;
Lee, Yongseok ;
Kang, Jungmin ;
Park, Inchul ;
Myung, Seung-Taek ;
Kim, Jongsoon .
ENERGY STORAGE MATERIALS, 2020, 28 :47-54
[24]   1D Nanostructured Na7V4(P2O7)4(PO4) as High-Potential and Superior-Performance Cathode Material for Sodium-Ion Batteries [J].
Deng, Chao ;
Zhang, Sen .
ACS APPLIED MATERIALS & INTERFACES, 2014, 6 (12) :9111-9117
[25]   Crystal structures and sodium/silver distributions within the ionic conductors Na5Ag2Fe3(As2O7)4 and Na2Ag5Fe3(P2O7)4 [J].
Quarez, Eric ;
Mentre, Olivier ;
Djellab, Karim ;
Masquelier, Christian .
NEW JOURNAL OF CHEMISTRY, 2010, 34 (02) :287-293
[26]   A comparative study of structure, air sensitivity and electrochemistry of sodium iron pyrophosphates Na2-xFe1+x/2P2O7 ( x=0; 0.44) [J].
Kosova, Nina V. ;
Rezepova, Daria O. ;
Podgornova, Olga A. ;
Slobodyuk, Arseny B. ;
Petrov, Sergey A. ;
Avdeev, Maxim .
ELECTROCHIMICA ACTA, 2017, 235 :42-55
[27]   Synthesis and characterization of a crystalline Na4Fe3(PO4)2(P2O7) cathode material for sodium-ion batteries [J].
Subasi, Yaprak ;
Altenschmidt, Laura ;
Lindgren, Fredrik ;
Ericsson, Tore ;
Haggstrom, Lennart ;
Tai, Cheuk-Wai ;
Liu, Haidong ;
Younesi, Reza .
JOURNAL OF MATERIALS CHEMISTRY A, 2024, 12 (35) :23506-23517
[28]   Unlocking the Potential: Na4Fe3(PO4)2(P2O7) Supporting the Innovation of Commercial Sodium-Ion Batteries [J].
Liu, Cong ;
Zhang, Zhi ;
Liao, Huanyi ;
Jiang, Yumeng ;
Zheng, Yifan ;
Li, Zhongxi ;
Gao, Yihua .
ADVANCED FUNCTIONAL MATERIALS, 2025, 35 (23)
[29]   Na3.12Fe2.44(P2O7)2/multi-walled carbon nanotube composite as a cathode material for sodium-ion batteries [J].
Niu, Yubin ;
Xu, Maowen ;
Cheng, Chuanjun ;
Bao, ShuJuan ;
Hou, Junke ;
Liu, Sangui ;
Yi, Fenglian ;
He, Hong ;
Li, Chang Ming .
JOURNAL OF MATERIALS CHEMISTRY A, 2015, 3 (33) :17224-17229
[30]   Porous graphene to encapsulate Na6.24Fe4.88(P2O7)4 as composite cathode materials for Na-ion batteries [J].
Niu, Yubin ;
Xu, Maowen ;
Bao, Shu-Juan ;
Li, Chang Ming .
CHEMICAL COMMUNICATIONS, 2015, 51 (66) :13120-13122
12345