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Type II germanium clathrates have recently been investigated for potential applications as anodes in batteries due to their cage-like structures that can accommodate electrochemical insertion of guest ions. To synthesize type II Ge clathrates (Ge136), several experimental routes use thermal or electrochemical desodiation of the Zintl phase compound Na4Ge4. However, the mechanism by which Na atoms are removed from the precursor to form clathrates is not well understood. Herein, we use first-principles density functional theory and nudged elastic band calculations to understand the reaction mechanism and formation energies of the products typically observed in the synthesis, namely, NaδGe136 (0 < δ < 24) type II clathrates and hexagonal phase Na1–xGe3+z. Specifically, we confirm the energetic feasibility of Na vacancy formation in Na4Ge4 and find that the barrier for Na vacancy migration is only 0.37 eV. This relatively low energy barrier is consistent with the ease with which Na4Ge4 can be desodiated to form the products. We also discuss the energetics, sodium migration pathways, and potential electrochemical performance of Ge136 as anode material for Na-ion batteries. Overall, this study highlights how first-principles calculations can be used to understand the synthesis mechanism and desodiation processes in clathrate materials and will help guide researchers in the design and evaluation of new open framework compounds as viable materials for energy storage applications. 

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.