The guest‐free, type‐II Si clathrate (Si136) is an open cage polymorph of Si with structural features amenable to electrochemical Li storage. However, the detailed mechanism for reversible Li insertion and migration within the vacant cages of Si136is not established. Herein, X‐ray characterization and density functional theory (DFT) calculations are used to understand the structural origin of electrochemical Li insertion into the type‐II clathrate structure. At low Li content, instead of alloying with Si, topotactic Li insertion into the empty cages occurs at ≈0.3 V versus Li/Li+with a capacity of ≈231 mAh g−1(corresponding to composition Li32Si136). A synchrotron powder X‐ray diffraction analysis of electrodes after lithiation shows evidence of Li occupation within the Si20and Si28cages and a volume expansion of 0.22%, which is corroborated by DFT calculations. Nudged elastic band calculations suggest a low barrier (0.2 eV) for Li migration through interconnected Si28cages, whereas there is a higher barrier for Li migration into Si20cages (2.0 eV). However, if Li is present in a neighboring cage, a cooperative migration pathway with a barrier of 0.65 eV is possible. The results show that the type‐II Si clathrate displays unique electrochemical properties for potential applications as Li‐ion battery anodes.
- NSF-PAR ID:
- 10236975
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Energy and Sustainability Research
- Volume:
- 2
- Issue:
- 5
- ISSN:
- 2699-9412
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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