TY - JOUR
T1 - Understanding the Amorphous Lithiation Pathway of the Type i Ba8Ge43Clathrate with Synchrotron X-ray Characterization
AU - Dopilka, Andrew
AU - Childs, Amanda
AU - Bobev, Svilen
AU - Chan, Candace K.
N1 - Funding Information:
This work was supported by funding from NSF DMR-1710017 and NSF DMR-1709813. A.D. acknowledges support from ASU Fulton Schools of Engineering Dean’s Fellowships. C.K.C. acknowledges support from the Max Planck Society and the Alexander von Humboldt Foundation for a Humboldt Research Fellowship. The authors greatly acknowledge the use of facilities within the Eyring Materials Center at Arizona State University supported in part by NNCI-ECCS-1542160. The authors also thank the Diamond Light Source (Didcot, UK) for access to beamline I15-1 (proposal nos. EE21467 and CY22209), T. Forrest and D. Keeble for assistance with PDF measurements, Deutsches Elektronen-Synchrotron (Hamburg, Germany) for access to beamline P02.1 (proposal no. I-20180707), and J. Tseng for assistance with in situ heating XRD measurements.
Publisher Copyright:
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PY - 2020/11/10
Y1 - 2020/11/10
N2 - Tetrel (Tt = Si, Ge, and Sn) clathrates have highly tunable host-guest structures and have been investigated as novel electrode materials for Li-ion batteries. However, there is little understanding of how the clathrate structure affects the lithiation processes and phase evolution. Herein, the electrochemical lithiation pathway of type I clathrate Ba8Ge43 is investigated with synchrotron X-ray diffraction (XRD) and pair distribution function (PDF) analyses and compared to the lithiation of germanium with a diamond cubic structure (α-Ge). The results confirm previous laboratory XRD studies showing that Ba8Ge43 goes through a solely amorphous phase transformation, which contrasts with the crystalline phase transformations that take place during lithiation of micrometer-sized α-Ge particles. The local structure of framework-substituted clathrate Ba8Al16Ge30 after lithiation is found to proceed through an amorphous phase transformation similar to that in Ba8Ge43. In situ PDF and XRD during heating show that the amorphous phases derived from lithiation of Ba8Ge43 are structurally related to various Li-Ge phases and crystallize at low temperatures (350-420 K). We conclude that the Ba atoms inside the clathrate structure act to break up the long-range ordering of Li-Ge clusters and kinetically prevent the nucleation and growth of bulk crystalline phases. The amorphous phase evolution of the clathrate structure during lithiation results in electrochemical properties distinct from those in α-Ge, such as a single-phase reaction mechanism and lower voltage, suggesting possible advantages of clathrates over elemental phases for use as anodes in Li-ion batteries.
AB - Tetrel (Tt = Si, Ge, and Sn) clathrates have highly tunable host-guest structures and have been investigated as novel electrode materials for Li-ion batteries. However, there is little understanding of how the clathrate structure affects the lithiation processes and phase evolution. Herein, the electrochemical lithiation pathway of type I clathrate Ba8Ge43 is investigated with synchrotron X-ray diffraction (XRD) and pair distribution function (PDF) analyses and compared to the lithiation of germanium with a diamond cubic structure (α-Ge). The results confirm previous laboratory XRD studies showing that Ba8Ge43 goes through a solely amorphous phase transformation, which contrasts with the crystalline phase transformations that take place during lithiation of micrometer-sized α-Ge particles. The local structure of framework-substituted clathrate Ba8Al16Ge30 after lithiation is found to proceed through an amorphous phase transformation similar to that in Ba8Ge43. In situ PDF and XRD during heating show that the amorphous phases derived from lithiation of Ba8Ge43 are structurally related to various Li-Ge phases and crystallize at low temperatures (350-420 K). We conclude that the Ba atoms inside the clathrate structure act to break up the long-range ordering of Li-Ge clusters and kinetically prevent the nucleation and growth of bulk crystalline phases. The amorphous phase evolution of the clathrate structure during lithiation results in electrochemical properties distinct from those in α-Ge, such as a single-phase reaction mechanism and lower voltage, suggesting possible advantages of clathrates over elemental phases for use as anodes in Li-ion batteries.
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U2 - 10.1021/acs.chemmater.0c03641
DO - 10.1021/acs.chemmater.0c03641
M3 - Article
AN - SCOPUS:85095982060
SN - 0897-4756
VL - 32
SP - 9444
EP - 9457
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 21
ER -