Tuning Magnetic Symmetry and Properties in the Olivine Series Li1–xFexMn1–xPO4 through Selective Delithiation

Diethrich, Timothy J.; Gnewuch, Stephanie; Dold, Kaitlyn G.; Taddei, Keith M.; Rodriguez, Efrain E.

doi:10.1021/acs.chemmater.2c00372

Tuning Magnetic Symmetry and Properties in the Olivine Series Li_1–xFe_xMn_1–xPO₄ through Selective Delithiation

Journal Article · Fri May 20 00:00:00 EDT 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.2c00372· OSTI ID:1885254

^[1]; ^[1]; Dold, Kaitlyn G. ^[1]; ^[2]; ^[1]

Univ. of Maryland, College Park, MD (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

In this work, we present the first in-depth study of the nuclear and magnetic structures of the fully lithiated LiFe_xMn_1–xPO₄ solid solutions as well as the partially delithiated Li_1–xFe_xMn_1–xPO₄ series using neutron powder diffraction. By using a weak oxidizing solution that only oxidizes Fe²⁺, we find that lithium can be removed from these olivines in a stepwise manner. Representational analysis was performed on the observed magnetic reflections and found that the lithiated solid solutions order in the magnetic space group Pnma', which is identical to triphylite (LiFePO₄). We report that, even when removing 20% of the lithium from the hcp lattice, the magnetic structure changes and multiple magnetic contributions are needed to fully encompass the observed magnetic order. We find that the partially delithiated x = 0.2 and 0.3 have a magnetic structure P2₁'/n11, and when x surpasses 0.3, the magnetic structure changes to P2₁2₁2₁. We give a detailed report on the effect of delithiation on magnetic order, bond distances/angles, and the super- and supersuperexchange interactions in the material. The symmetries of the magnetic order of these solid solutions are then discussed with regard to their potential as ferrotoroidic candidates.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; SC0016434

OSTI ID:: 1885254

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 11 Vol. 34; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Tuning Magnetic Symmetry and Properties in the Olivine Series Li1–xFexMn1–xPO4 through Selective Delithiation

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Tuning Magnetic Symmetry and Properties in the Olivine Series Li_1–xFe_xMn_1–xPO₄ through Selective Delithiation