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Title: Nanoscale Detection of Intermediate Solid Solutions in Equilibrated Li xFePO 4 Microcrystals

Redox-driven phase transformations in solids determine the performance of lithium-ion batteries, crucial in the technological transition from fossil fuels. Couplings between chemistry and strain define reversibility and fatigue of an electrode. The accurate definition of all phases in the transformation, their energetics, and nanoscale location within a particle produces fundamental understanding of these couplings needed to design materials with ultimate performance. In this paper we demonstrate that scanning X-ray diffraction microscopy (SXDM) extends our ability to image battery processes in single particles. In LiFePO 4 crystals equilibrated after delithiation, SXDM revealed the existence of domains of miscibility between LiFePO 4 and Li 0.6FePO 4. These solid solutions are conventionally thought to be metastable, and were previously undetected by spectromicroscopy. The observation provides experimental verification of predictions that the LiFePO 4–FePO 4 phase diagram can be altered by coherency strain under certain interfacial orientations. Finally, it enriches our understanding of the interaction between diffusion, chemistry, and mechanics in solid state transformations.
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [5] ; ORCiD logo [4] ; ORCiD logo [1]
  1. Univ. of Illinois, Chicago, IL (United States). Dept. of Chemistry
  2. Univ. of Illinois, Chicago, IL (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Division
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  4. Univ. of Cambridge (United Kingdom). Dept. of Chemistry
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Division
Publication Date:
Grant/Contract Number:
AC02-06CH11357; AC02-76SF00515; SC0012583
Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 17; Journal Issue: 12; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Illinois, Chicago, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Li-ion battery materials; LiFePO4; nanoscale chemical imaging; redox phase transitions
OSTI Identifier:
1461313

May, Brian M., Yu, Young-Sang, Holt, Martin V., Strobridge, Fiona C., Boesenberg, Ulrike, Grey, Clare P., and Cabana, Jordi. Nanoscale Detection of Intermediate Solid Solutions in Equilibrated LixFePO4 Microcrystals. United States: N. p., Web. doi:10.1021/acs.nanolett.7b03086.
May, Brian M., Yu, Young-Sang, Holt, Martin V., Strobridge, Fiona C., Boesenberg, Ulrike, Grey, Clare P., & Cabana, Jordi. Nanoscale Detection of Intermediate Solid Solutions in Equilibrated LixFePO4 Microcrystals. United States. doi:10.1021/acs.nanolett.7b03086.
May, Brian M., Yu, Young-Sang, Holt, Martin V., Strobridge, Fiona C., Boesenberg, Ulrike, Grey, Clare P., and Cabana, Jordi. 2017. "Nanoscale Detection of Intermediate Solid Solutions in Equilibrated LixFePO4 Microcrystals". United States. doi:10.1021/acs.nanolett.7b03086. https://www.osti.gov/servlets/purl/1461313.
@article{osti_1461313,
title = {Nanoscale Detection of Intermediate Solid Solutions in Equilibrated LixFePO4 Microcrystals},
author = {May, Brian M. and Yu, Young-Sang and Holt, Martin V. and Strobridge, Fiona C. and Boesenberg, Ulrike and Grey, Clare P. and Cabana, Jordi},
abstractNote = {Redox-driven phase transformations in solids determine the performance of lithium-ion batteries, crucial in the technological transition from fossil fuels. Couplings between chemistry and strain define reversibility and fatigue of an electrode. The accurate definition of all phases in the transformation, their energetics, and nanoscale location within a particle produces fundamental understanding of these couplings needed to design materials with ultimate performance. In this paper we demonstrate that scanning X-ray diffraction microscopy (SXDM) extends our ability to image battery processes in single particles. In LiFePO4 crystals equilibrated after delithiation, SXDM revealed the existence of domains of miscibility between LiFePO4 and Li0.6FePO4. These solid solutions are conventionally thought to be metastable, and were previously undetected by spectromicroscopy. The observation provides experimental verification of predictions that the LiFePO4–FePO4 phase diagram can be altered by coherency strain under certain interfacial orientations. Finally, it enriches our understanding of the interaction between diffusion, chemistry, and mechanics in solid state transformations.},
doi = {10.1021/acs.nanolett.7b03086},
journal = {Nano Letters},
number = 12,
volume = 17,
place = {United States},
year = {2017},
month = {11}
}