Title: From Layered Antiferromagnet to 3D Ferromagnet: LiMnBi-to-MnBi Magneto-Structural Transformation

Abstract

Here, the intermetallic compound LiMnBi was synthesized by the two-step solid-state reaction from the elements. The synthesis temperature of 850 K was selected based on in-situ high-temperature powder X-ray diffraction data. LiMnBi crystalizes in the layered-like PbClF structure type (a = 4.3131(7) Å, c = 7.096(1) Å at 100 K, P4/nmm space group, Z = 2). LiMnBi structure is built of the alternating [MnBi] and Li layers, as determined from single-crystal X-ray diffraction data. Magnetic properties measurements and solid-state ⁷Li Nuclear Magnetic Resonance data collected for polycrystalline LiMnBi samples indicate the long-range antiferromagnetic ordering of Mn sublattice at ~340 K, with no superconductivity down to 5 K detected. LiMnBi is air- and water-sensitive. In aerobic conditions, Li can be extracted from LiMnBi structure to form Li₂O/LiOH and MnBi (NiAs structure type, P6₃/mmc). The obtained MnBi polymorph was previously reported to be one of the strongest rare-earth-free ferromagnets, yet its bulk synthesis in powder form is cumbersome. The proposed magneto-structural transformation from ternary LiMnBi to ferromagnetic MnBi involves condensation of the MnBi4 tetrahedra upon Li deintercalation and is exclusive to LiMnBi. In contrast, ferromagnetic MnBi cannot be obtained from either isostructural NaMnBi and KMnBi, or from the structurally related CaMn₂Bi₂. Suchmore » a distinctive transformation in the case of LiMnBi is presumed to be due to its fitting reactivity to yield MnBi and favorable interlayer distance between [MnBi] layers, while the interlayer distance in NaMnBi and KMnBi structural analogs is unfavorably long. The studies of delithiation from the layered-like LiMnBi under different chemical environments indicate that the yield of the MnBi depends on the type of solvent used and the kinetics of the reaction. A slow rate and mild reaction media lead to a high fraction of the MnBi product. The saturation magnetization of the “as-prepared” MnBi is ~50 % of the expected value of 81.3 emu/g. Overall, this study adds a missing member to the family of ternary pnictides and illustrates how soft-chemistry methods can be used to obtain “difficult-to-synthesize” compounds.« less

Authors:

Gvozdetskyi, Volodymyr ^[1]; Rana, Khusboo ^[2]; Ribeiro, Raquel A. ^[3]; Mantravadi, Aishwarya ^[3]; Adeyemi, Adedoyin N. ^[3]; Wang, Renhai ^[4]; Dong, Huafeng ^[4]; Ho, Kai-Ming ^[3]; Furukawa, Yuji ^[2]; Canfield, Paul C. ^[2]; Zaikina, Julia V.  ^[3]

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+ Show Author Affiliations

1. Iowa State Univ., Ames, IA (United States); Univ. of Alberta, Edmonton, AB (Canada)
2. Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States)
3. Iowa State Univ., Ames, IA (United States)
4. Guangdong University of Technology, Guangzhou (China)

Publication Date:

Thu Apr 06 00:00:00 EDT 2023

Research Org.:

Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); National Science Foundation (NSF); Guangdong Basic and Applied Basic Research Foundation

OSTI Identifier:

1972805

Report Number(s):

IS-J 11,034
Journal ID: ISSN 0897-4756

Grant/Contract Number:  

AC02-07CH11358; DMR-1944551; 2021A1515110328; 2022A1515012174

Resource Type:

Accepted Manuscript

Journal Name:

Chemistry of Materials

Additional Journal Information:

Journal Volume: 35; Journal Issue: 8; Journal ID: ISSN 0897-4756

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Crystal structure; Diffraction; Magnetic properties; Organic reactions; Transition metals