The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals

Lininger, Christianna N.; Bruck, Andrea M.; Lutz, Diana M.; Housel, Lisa M.; Takeuchi, Kenneth J.; Takeuchi, Esther S.; Huq, Ashfia; Marschilok, Amy C.; West, Alan C.

doi:10.1002/adfm.201907337

Title: The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals

Journal Article · 20 November 2019 · Advanced Functional Materials

DOI: https://doi.org/10.1002/adfm.201907337 · OSTI ID:1580038

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Columbia Univ., New York, NY (United States); Univ. of California, Berkeley, CA (United States)
Stony Brook Univ., Stony Brook, NY (United States)
Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Columbia Univ., New York, NY (United States)

Abstract Nanostructured materials can exhibit phase change behavior that deviates from the macroscopic phase behavior. This is exemplified by the ambiguity for the equilibrium phases driving the first open‐circuit voltage (OCV) plateau for the lithiation of Fe ₃ O ₄ nanocrystals. Adding complexity, the relaxed state for Li _x Fe ₃ O ₄ is observed to be a function of electrochemical discharge rate. The phases occurring on the first OCV plateau for the lithiation of Fe ₃ O ₄ nanocrystals have been investigated with density functional theory (DFT) through the evaluation of stable, or hypothesized metastable, reaction pathways. Hypotheses are evaluated through the systematic combined refinement with X‐ray absorption spectroscopy (XAS), X‐ray diffraction (XRD) measurements, neutron‐diffraction measurements, and the measured OCV on samples lithiated to x = 2.0, 3.0, and 4.0 in Li _x Fe ₃ O ₄ . In contrast to the Li–Fe–O bulk phase thermodynamic pathway, Fe ⁰ is not observed as a product on the first OCV plateau for 10–45 nm nanocrystals. The phase most consistent with the systematic refinement is LiFe ₃ O ₄ , showing Li+Fe cation disorder. The observed equilibrium concentration for conversion to Fe ⁰ occurs at x = 4.0. These definitive phase identifications rely heavily on the systematic combined refinement approach, which is broadly applicable to other nano‐ and mesoscaled systems that have suffered from difficult or crystallite‐size‐dependent phase identification.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: SC0012704; SC0012673; C090171; ACI-1548562; TG-DMR160174; TG-DMR160128; AC02-06CH11357

OSTI ID:: 1580038

Alternate ID(s):: OSTI ID: 1595869

Report Number(s):: BNL-212447-2019-JAAM

Journal Information:: Advanced Functional Materials, Vol. 30, Issue 5; ISSN 1616-301X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 7 works

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