TY - JOUR
T1 - Electrochemical Lithium Alloying Behavior of Guest-Free Type II Silicon Clathrates
AU - Dopilka, Andrew
AU - Childs, Amanda
AU - Bobev, Svilen
AU - Chan, Candace K.
N1 - Funding Information:
This work was supported by funding from NSF from the awards DMR-1206795, DMR-1710017, DMR-1709813, DMR-2004514, and DMR-2004579. 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 also thank the Diamond Light Source (Didcot, UK) for access to beamline I15-1 (proposal no. CY22209) and T. Forrest and D. Keeble for assistance with PDF measurements. The authors also thank Deutsches Elektronen-Synchrotron (Hamburg, Germany) for access to beamline P02.1 (proposal no. I-20180707) and J. Tseng for assistance with synchrotron XRD measurements.
Funding Information:
Open access funded by Max Planck Society.
Publisher Copyright:
© 2021 The Authors. Published by American Chemical Society
PY - 2021/9/9
Y1 - 2021/9/9
N2 - The guest-free type II Si clathrate (Si136) is an open framework polymorph of Si that displays unique electrochemical reactions with Li. Li ions are first topotactically inserted into the vacant clathrate cages, followed by an alloying reaction that forms an amorphous lithium silicide phase. The alloying reaction voltage is higher than those seen in other Si electrodes, suggesting that there are structural differences in the formed amorphous phases. Synchrotron X-ray total scattering measurements and pair distribution function analysis are employed to characterize the amorphous phases formed after lithiation. The results show that the clathrate becomes completely amorphous at an earlier stage of lithiation when compared to diamond cubic Si, forming a phase with comparatively larger amounts of Si-Si bonding. The initial insertion of Li into the clathrate cages establishes important Li diffusion paths that kinetically enable the formation of an amorphous phase with lower Li content than typically seen in other silicon-based electrodes. After the initial crystalline-to-amorphous conversion reaction, lithiation takes place via solid-solution alloying. These results demonstrate how the topotactic insertion of Li into an alloying host can kinetically enable modified reaction pathways leading to more homogeneous lithiation throughout the electrode, which is beneficial for Li-ion battery applications.
AB - The guest-free type II Si clathrate (Si136) is an open framework polymorph of Si that displays unique electrochemical reactions with Li. Li ions are first topotactically inserted into the vacant clathrate cages, followed by an alloying reaction that forms an amorphous lithium silicide phase. The alloying reaction voltage is higher than those seen in other Si electrodes, suggesting that there are structural differences in the formed amorphous phases. Synchrotron X-ray total scattering measurements and pair distribution function analysis are employed to characterize the amorphous phases formed after lithiation. The results show that the clathrate becomes completely amorphous at an earlier stage of lithiation when compared to diamond cubic Si, forming a phase with comparatively larger amounts of Si-Si bonding. The initial insertion of Li into the clathrate cages establishes important Li diffusion paths that kinetically enable the formation of an amorphous phase with lower Li content than typically seen in other silicon-based electrodes. After the initial crystalline-to-amorphous conversion reaction, lithiation takes place via solid-solution alloying. These results demonstrate how the topotactic insertion of Li into an alloying host can kinetically enable modified reaction pathways leading to more homogeneous lithiation throughout the electrode, which is beneficial for Li-ion battery applications.
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U2 - 10.1021/acs.jpcc.1c04020
DO - 10.1021/acs.jpcc.1c04020
M3 - Article
AN - SCOPUS:85114625918
SN - 1932-7447
VL - 125
SP - 19110
EP - 19118
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 35
ER -