Nanoscale Detection of Intermediate Solid Solutions in Equilibrated LixFePO4 Microcrystals

May, Brian M.; Yu, Young-Sang; Holt, Martin V.; Strobridge, Fiona C.; Boesenberg, Ulrike; Grey, Clare P.; Cabana, Jordi

doi:10.1021/acs.nanolett.7b03086

Title: Nanoscale Detection of Intermediate Solid Solutions in Equilibrated Li_xFePO₄ Microcrystals

Journal Article · Wed Nov 22 00:00:00 EST 2017 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.7b03086· OSTI ID:1461313

May, Brian M. ^[1]; Yu, Young-Sang ^[2]; Holt, Martin V. ^[3]; Strobridge, Fiona C. ^[4]; Boesenberg, Ulrike ^[5];

^[4];

^[1]

Univ. of Illinois, Chicago, IL (United States). Dept. of Chemistry
Univ. of Illinois, Chicago, IL (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Division
Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
Univ. of Cambridge (United Kingdom). Dept. of Chemistry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Division

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 Li_0.6FePO₄. 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.

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Research Organization:: Argonne National Laboratory (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 Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; AC02-76SF00515; SC0012583

OSTI ID:: 1461313

Journal Information:: Nano Letters, Vol. 17, Issue 12; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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