Mesoscale Phase Distribution in Single Particles of LiFePO4 following Lithium Deintercalation

被引：103

作者：

Boesenberg, Ulrike ^{[1
]}

Meirer, Florian ^{[2
]}

Liu, Yijin ^{[3
]}

Shukla, Alpesh K. ^{[1
]}

Dell'Anna, Rossana ^{[2
]}

Tyliszczak, Tolek ^{[4
]}

Chen, Guoying ^{[1
]}

Andrews, Joy C. ^{[3
]}

Richardson, Thomas J. ^{[1
]}

Kostecki, Robert ^{[1
]}

Cabana, Jordi ^{[1
]}

机构：

[1] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Environm Energy Technol Div, Berkeley, CA 94720 USA

[2] Fdn Bruno Kessler, Ctr Mat & Microsyst, I-38050 Trento, Italy

[3] SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA

[4] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Adv Light Source, Berkeley, CA 94720 USA

来源：

CHEMISTRY OF MATERIALS | 2013年 / 25卷 / 09期

基金：

美国国家卫生研究院;

关键词：

intercalation reactions; chemical imaging battery electrode materials; LiFePO4; X-RAY MICROSCOPY; IN-SITU; COHERENCY STRAIN; MISCIBILITY GAP; SOLID-SOLUTION; ENERGY; TRANSFORMATIONS; NANOSCALE; KINETICS; SPECTROMICROSCOPY;

D O I：

10.1021/cm400106k

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The chemical phase distribution in hydrothermally grown micrometric single crystals of LiFePO4 following partial chemical delithiation was investigated. Full field and scanning X-ray microscopy were combined with X-ray absorption spectroscopy at the Fe and O K-edges, respectively, to produce maps with high chemical and spatial resolution. The resulting information was compared to morphological insight into the mechanics of the transformation by scanning transmission electron microscopy. This study revealed the interplay at the mesocale between microstructure and phase distribution during the redox process, as morphological defects were found to kinetically determine the progress of the reaction. Lithium deintercalation was also found to induce severe mechanical damage in the crystals, presumably due to the lattice mismatch between LiFePO4 and FePO4. Our results lead to the conclusion that rational design of intercalation-based electrode materials, such as LiFePO4, with optimized utilization and life requires the tailoring of particles that minimize kinetic barriers and mechanical strain. Coupling TXM-XANES with TEM can provide unique insight into the behavior of electrode materials during operation, at scales spanning from nanoparticles to ensembles and complex architectures.

引用

页码：1664 / 1672

页数：9

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