In situ Raman spectroscopy of LiFePO4: Size and morphology dependence during charge and self-discharge

Jing Wu, Gopi Krishna Phani Dathar, Chunwen Sun, Murali G. Theivanayagam, Danielle Applestone, Anthony G. Dylla, Arumugam Manthiram, Graeme Henkelman, John B. Goodenough, Keith J. Stevenson

Research output: Contribution to journalArticlepeer-review

61 Citations (Scopus)

Abstract

Previous studies of the size dependent properties of LiFePO4 have focused on the diffusion rate or phase transformation pathways by bulk analysis techniques such as x-ray diffraction (XRD), neutron diffraction and electrochemistry. In this work, in situ Raman spectroscopy was used to study the surface phase change during charge and self-discharge on a more localized scale for three morphologies of LiFePO4: (1) 25 ± 6 nm width nanorods, (2) 225 ± 6 nm width nanorods and (3) ∼2 μm porous microspheres. Both the large nanorod and microsphere geometries showed incomplete delithiation at the end of charge, which was most likely caused by anti-site defects along the 1D diffusion channels in the bulk of the larger particles. Based on the in situ Raman measurements, all of the morphologies studied exhibited self-discharge with time. Among them, the smallest FePO 4 particles self-discharged (lithiated) the fastest. While nanostructuring LiFePO4 can offer advantages in terms of lowering anti-site defects within particles, it also creates new problems due to high surface energies that allow self-discharge. The in situ Raman spectroscopy also showed that carbon coating did not provide significant improvement to the stability of the lithiated particles.

Original languageEnglish
Article number424009
JournalNanotechnology
Volume24
Issue number42
DOIs
Publication statusPublished - 25 Oct 2013
Externally publishedYes

Fingerprint

Dive into the research topics of 'In situ Raman spectroscopy of LiFePO4: Size and morphology dependence during charge and self-discharge'. Together they form a unique fingerprint.

Cite this