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

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 3O 4 nanocrystals. Adding complexity, the relaxed state for Li xFe 3O 4 is observed to be a function of electrochemical discharge rate. The phases occurring on the first OCV plateau for the lithiation of Fe 3O 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 xFe 3O 4. In contrast to the Li–Fe–O bulk phase thermodynamic pathway, Fe0 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 3O 4, showing Li+Fe cation disorder. Here, 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, whichmore » is broadly applicable to other nano– and mesoscaled systems that have suffered from difficult or crystallite–size–dependent phase identification.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [5]
  1. Columbia Univ., New York, NY (United States); Univ. of California, Berkeley, CA (United States)
  2. Stony Brook Univ., Stony Brook, NY (United States)
  3. Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. Columbia Univ., New York, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1580038
Alternate Identifier(s):
OSTI ID: 1595869
Report Number(s):
BNL-212447-2019-JAAM
Journal ID: ISSN 1616-301X
Grant/Contract Number:  
SC0012704; SC0012673; C090171; ACI-1548562; TG-DMR160174; TG-DMR160128; AC02-06CH11357; DE‐SC0012673; DE‐AC02‐06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Name: Advanced Functional Materials; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; batteries; lithium ions; nanomaterials; phase identification; thermodynamics

Citation Formats

Lininger, Christianna N., Bruck, Andrea M., Lutz, Diana M., Housel, Lisa M., Takeuchi, Kenneth J., Takeuchi, Esther S., Huq, Ashfia, Marschilok, Amy C., and West, Alan C. The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals. United States: N. p., 2019. Web. doi:10.1002/adfm.201907337.
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. The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals. United States. doi:10.1002/adfm.201907337.
Lininger, Christianna N., Bruck, Andrea M., Lutz, Diana M., Housel, Lisa M., Takeuchi, Kenneth J., Takeuchi, Esther S., Huq, Ashfia, Marschilok, Amy C., and West, Alan C. Wed . "The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals". United States. doi:10.1002/adfm.201907337.
@article{osti_1580038,
title = {The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals},
author = {Lininger, Christianna N. and Bruck, Andrea M. and Lutz, Diana M. and Housel, Lisa M. and Takeuchi, Kenneth J. and Takeuchi, Esther S. and Huq, Ashfia and Marschilok, Amy C. and West, Alan C.},
abstractNote = {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 Fe3O4 nanocrystals. Adding complexity, the relaxed state for LixFe3O4 is observed to be a function of electrochemical discharge rate. The phases occurring on the first OCV plateau for the lithiation of Fe3O4 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 LixFe3O4. In contrast to the Li–Fe–O bulk phase thermodynamic pathway, Fe0 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 LiFe3O4, showing Li+Fe cation disorder. Here, the observed equilibrium concentration for conversion to Fe0 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.},
doi = {10.1002/adfm.201907337},
journal = {Advanced Functional Materials},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {11}
}

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