Magnetic structure and properties of NaFePO4 polymorphs: antiferromagnetic ordering and spin-flop transition

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IOP Publishing
In recent years, the cost and sustainability concerns have renewed research efforts on sodium-ion batteries, propelling investigation on various layered oxides and polyanionic family of insertion compounds for low-cost and large-scale cathode applications. These cathode insertion compounds are functional materials, involving redox active 3d transition metals (e.g. Fe/Co/Ni) that are often magnetic in nature. During the Na (de)insertion process involving redox reaction of transition metals and structural alteration, the magnetic magnetic structure/ properties can vary significantly. We have investigated the magnetic structure and properties of NaFePO4 polyanionic system, which exists in two distinct polymorphs: metastable triphylite and stable maricite. The details of these structures are shown in the figure. Both these polymoprhs undergo antiferromagnetic ordering below 50 K (for triphylite) and 13 K (for maricite). Using the magnetic susceptibility, heat capacity and low temperature neutron powder diffraction, the magnetic structure of these two distinct polymorphs have been solved. The details of these antiferromagnetic structures will be described considering the super- and super-superexchange interactions. In addition, investigating the maricite NaFePO4 polymorph, which consists of edge-sharing FeO6 octahedral chains, we have discovered the occurrence of spin-flop transition below 40 kOe using susceptibility measurement and low-temperature Mossbauer spectroscopy. This spin-flopping (or metamagnetism) phenomenon in maricite NaFePO4 will be described in detail [1-5] to showcase the rich magnetism present in NaFePO4 insertion materials. © 2014 ECS - The Electrochemical Society
ECS Meeting Abstracts contain extended abstracts of the technical papers presented at ECS meetings and ECS-sponsored meetings. This publication offers a first look into the current research in the field. ECS Meeting Abstracts are freely available to all visitors to the ECS Digital Library.
Electric batteries, Cathodes, Oxides, Redox reactions, Transition elements, Magnetic properties
Barpanda, P., Avdeev, M., & Ling, C. D. (2014). Magnetic structure and properties of NaFePO4 polymorphs: antiferromagnetic ordering and spin-flop transition. Presented at 2014 ECS and SMEQ Joint International Meeting October 5-9, 2014, Cancun, Mexico. In ECS Meeting Abstracts, MA2014-02, A2-Batteries Beyond Lithium Ion. doi:10.1149/MA2014-02/2/110