Monoclinic α-Na2FePO4F with Strong Antisite Disorder and Enhanced Na+ Diffusion

被引：15

作者：

Kirsanova, Maria A. ^{[4
]}

Akmaev, Alexey S. ^{[1
]}

Aksyonov, Dmitry A. ^{[1
]}

Ryazantsev, Sergey, V ^{[1
]}

Nikitina, Victoria A. ^{[1
]}

Filimonov, Dmitry S. ^{[2
]}

Avdeev, Maxim ^{[3
]}

Abakumov, Artem M. ^{[1
]}

机构：

[1] Skolkovo Inst Sci & Technol, Ctr Energy Sci & Technol, Moscow 121205, Russia

[2] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119991, Russia

[3] Australian Nucl Sci & Technol Org, Kirrawee Dc, NSW 2232, Australia

[4] Skolkovo Inst Sci & Technol, Adv Imaging Core Facil, Moscow 121205, Russia

来源：

INORGANIC CHEMISTRY | 2020年 / 59卷 / 22期

基金：

俄罗斯基础研究基金会;

关键词：

Diffusion - Metal ions - Neutron diffraction - Phosphorus compounds - Cathodes - Sodium-ion batteries - Iron compounds - Lithium-ion batteries - Metals - Crystal atomic structure - Sodium compounds;

D O I：

10.1021/acs.inorgchem.0c01961

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A new monoclinic alpha-polymorph of the Na2FePO4F fluoride-phosphate has been directly synthesized via a hydrothermal method for application in metal-ion batteries. The crystal structure of the as-prepared alpha-Na2FePO4F studied with powder X-ray and neutron diffraction (P2(1)/c, a = 13.6753(10) angstrom, b = 5.2503(2) angstrom, c = 13.7202(8) angstrom, beta = 120.230(4)degrees) demonstrates strong antisite disorder between the Na and Fe atoms. As revealed with DFT-based calculations, alpha-Na2FePO4F has low migration barriers for Na+ along the main pathway parallel to the b axis, and an additional diffusion bypass allowing the Na+ cations to go around the Na/Fe antisite defects. These results corroborate with the extremely high experimental Na-ion diffusion coefficient of (1-5).10(-11) cm(2).s(-1), which is 2 orders of magnitude higher than that for the orthorhombic beta-polymorph ((5(-10)).10(-13) cm(2).s(-1)). Being tested as a cathode material in Na- and Li-ion battery cells, monoclinic alpha-Na2FePO4F exhibits a reversible specific capacity of 90 and 80 mAh g(-1), respectively.

引用

页码：16225 / 16237

页数：13

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