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Single crystals of V6O13 were grown by chemical vapour treatment; thereafter electrochemically lithiated. The title compound was the first phase formed during electrochemical lithiation at 2.65 V versus Li/Li+. The Li2V6O13 structure can be described as layers of VO6 octahedra stacked perpendicular to the c direction. Lithiation causes a 7.6% expansion along the c axis. The lithium ions occupy positions with a fivefold square pyrimidal oxygen coordination between the layers.

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