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Volume 134, 2007
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Nanostructured materials for lithium-ion batteries: Surface conductivity vs. bulk ion/electron transport

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Abstract

Lithium metal phosphates are amongst the most promising cathode materials for high capacity lithium-ion batteries. Owing to their inherently low electronic conductivity, it is essential to optimize their properties to minimize defect concentration and crystallite size (down to the submicron level), control morphology, and to decorate the crystallite surfaces with conductive nanostructures that act as conduits to deliver electrons to the bulk lattice. Here, we discuss factors relating to doping and defects in olivine phosphates LiMPO4 (M = Fe, Mn, Co, Ni) and describe methods by which in situ nanophase composites with conductivities ranging from 10−4–10−2 S cm−1 can be prepared. These utilize surface reactivity to produce intergranular nitrides, phosphides, and/or phosphocarbides at temperatures as low as 600 °C that maximize the accessibility of the bulk for Li de/insertion. Surface modification can only address the transport problem in part, however. A key issue in these materials is also to unravel the factors governing ion and electron transport within the lattice. Lithium de/insertion in the phosphates is accompanied by two-phase transitions owing to poor solubility of the single phase compositions, where low mobility of the phase boundary limits the rate characteristics. Here we discuss concerted mobility of the charge carriers. Using Mössbauer spectroscopy to pinpoint the temperature at which the solid solution forms, we directly probe small polaron hopping in the solid solution LixFePO4 phases formed at elevated temperature, and give evidence for a strong correlation between electron and lithium delocalization events that suggests they are coupled.

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Publication details

The article was received on 22 Feb 2006, accepted on 09 May 2006 and first published on 07 Aug 2006


Article type: Paper
DOI: 10.1039/B602698B
Faraday Discuss., 2007,134, 119-141

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    Nanostructured materials for lithium-ion batteries: Surface conductivity vs. bulk ion/electron transport

    B. Ellis, P. Subramanya Herle, Y.-H. Rho, L. F. Nazar, R. Dunlap, L. K. Perry and D. H. Ryan, Faraday Discuss., 2007, 134, 119
    DOI: 10.1039/B602698B

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