Revision of the Li–Si Phase Diagram: Discovery and Single-Crystal X-ray Structure Determination of the High-Temperature Phase Li4.11Si

Silicon has been regarded as a promising anode material for future lithium-ion batteries, and Li–Si phases play an important role. A detailed reinvestigation of the Li-rich part of the binary Li–Si phase diagram revealed the existence of a new phase, Li4.106(2)Si (Li16.42Si4). Li16.42Si4 forms through the peritectic decomposition of the Li-richest phase Li17Si4 at 481–486 °C and was characterized by single-crystal X-ray diffraction (a = 4.5246(2) A, b = 21.944(1) A, c = 13.2001(6) A, space group Cmcm, Z = 16), differential scanning calorimetry, and theoretical calculations. Li16.42Si4 represents a high-temperature phase that is thermodynamically stable above ∼480 °C and decomposes peritectically at 618 ± 2 °C to Li13Si4 and a melt. Li16.42Si4 can be retained at room temperature. The structure consists of 3 and 10 different kinds of Si and Li atoms, respectively. Two Li positions show occupational disorder. Si atoms are well-separated from each other and have only Li atoms as nearest neighbors. This is sim...

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