Journal
SCIENCE
Volume 344, Issue 6191, Pages -Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.1252817
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Funding
- Northeastern Center for Chemical Energy Storage, an Energy Frontier Research Center - U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences [DE-SC0001294]
- DOE [DE-AC02-06CH11357]
- European Union [FP7-265368]
- Cambridge Overseas Trust
- Engineering Physical Science Research Council
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The absence of a phase transformation involving substantial structural rearrangements and large volume changes is generally considered to be a key characteristic underpinning the high-rate capability of any battery electrode material. In apparent contradiction, nanoparticulate LiFePO4, a commercially important cathode material, displays exceptionally high rates, whereas its lithium-composition phase diagram indicates that it should react via a kinetically limited, two-phase nucleation and growth process. Knowledge concerning the equilibrium phases is therefore insufficient, and direct investigation of the dynamic process is required. Using time-resolved in situ x-ray powder diffraction, we reveal the existence of a continuous metastable solid solution phase during rapid lithium extraction and insertion. This nonequilibrium facile phase transformation route provides a mechanism for realizing high-rate capability of electrode materials that operate via two-phase reactions.
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