IR near-field spectroscopy and imaging of single Li(x)FePO4 microcrystals.
This study demonstrates the unique capability of infrared near-field nanoscopy combined with Fourier transform infrared spectroscopy to map phase distributions in microcrystals of Li(x)FePO4, a positive electrode material for Li-ion batteries. Ex situ nanoscale IR imaging provides direct evidence for the coexistence of LiFePO4 and FePO4 phases in partially delithiated single-crystal microparticles. A quantitative three-dimensional tomographic reconstruction of the phase distribution within a single microcrystal provides new insights into the phase transformation and/or relaxation mechanism, revealing a FePO4 shell surrounding a diamond-shaped LiFePO4 inner core, gradually shrinking in size and vanishing upon delithiation of the crystal. The observed phase propagation pattern supports recent functional models of LiFePO4 operation relating electrochemical performance to material design. This work demonstrates the remarkable potential of near-field optical techniques for the characterization of electrochemical materials and interfaces.
Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
I T
IT
Lucas
A S
AS
McLeod
J S
JS
Syzdek
D S
DS
Middlemiss
C P
CP
Grey
D N
DN
Basov
R
R
Kostecki
D058085:Iron Compounds / Q000737:chemistry*; D018020:Lithium Compounds / Q000737:chemistry*; D010710:Phosphates / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared
D058085:Iron Compounds; D018020:Lithium Compounds; D010710:Phosphates
IR s-SNOM; Li-ion batteries; LiFePO4; phase distribution