Thermodynamically stable lithium silicides and germanides from density-functional theory calculations

Density-functional-theory (DFT) calculations have been performed on the Li-Si and Li-Ge systems. Lithiated Si and Ge, including their metastable phases, play an important technological r\^ole as Li-ion battery (LIB) anodes. The calculations comprise structural optimisations on crystal structures obtained by swapping atomic species to Li-Si and Li-Ge from the X-Y structures in the International Crystal Structure Database, where X={Li,Na,K,Rb,Cs} and Y={Si,Ge,Sn,Pb}. To complement this at various Li-Si and Li-Ge stoichiometries, ab initio random structure searching (AIRSS) was also performed. Between the ground-state stoichiometries, including the recently found Li$_{17}$Si$_{4}$ phase, the average voltages were calculated, indicating that germanium may be a safer alternative to silicon anodes in LIB, due to its higher lithium insertion voltage. Calculations predict high-density Li$_1$Si$_1$ and Li$_1$Ge$_1$ $P4/mmm$ layered phases which become the ground state above 2.5 and 5 GPa respectively and reveal silicon and germanium's propensity to form dumbbells in the Li$_x$Si, $x=2.33-3.25$ stoichiometry range. DFT predicts the stability of the Li$_{11}$Ge$_6$ $Cmmm$, Li$_{12}$Ge$_7$ $Pnma$ and Li$_7$Ge$_3$ $P32_12$ phases and several new Li-Ge compounds, with stoichiometries Li$_5$Ge$_2$, Li$_{13}$Ge$_5$, Li$_8$Ge$_3$ and Li$_{13}$Ge$_4$.Comment: 10 pages, 5 figure

Energetics of hydrogen/lithium complexes in silicon analyzed using the Maxwell construction

We have studied hydrogen/lithium complexes in crystalline silicon using density-functional-theory methods and the ab initio random structure searching (AIRSS) method for predicting structures. A method based on the Maxwell construction and convex hull diagrams is introduced which gives a graphical representation of the relative stabilities of point defects in a crystal and enables visualization of the changes in stability when the chemical potentials are altered. We have used this approach to study lithium and hydrogen impurities in silicon, which models aspects of the anode material in the recently-suggested lithium-ion batteries. We show that hydrogen may play a role in these anodes, finding that hydrogen atoms bind to three-atom lithium clusters in silicon, forming stable {H,3Li} and {2H,3Li} complexes, while the {H,2Li} complex is almost stable.Comment: (5 pages, 4 figures

Lithiation of silicon via lithium Zintl-defect complexes

An extensive search for low-energy lithium defects in crystalline silicon using density-functional-theory methods and the ab initio random structure searching (AIRSS) method shows that the four-lithium-atom substitutional point defect is exceptionally stable. This defect consists of four lithium atoms with strong ionic bonds to the four under-coordinated atoms of a silicon vacancy defect, similar to the bonding of metal ions in Zintl phases. This complex is stable over a range of silicon environments, indicating that it may aid amorphization of crystalline silicon and form upon delithiation of the silicon anode of a Li-ion rechargeable battery.Comment: 4 pages, 3 figure

Hydrodynamic induced deformation and orientation of a microscopic elastic filament

We describe simulations of a microscopic elastic filament immersed in a fluid and subject to a uniform external force. Our method accounts for the hydrodynamic coupling between the flow generated by the filament and the friction force it experiences. While models that neglect this coupling predict a drift in a straight configuration, our findings are very different. Notably, a force with a component perpendicular to the filament axis induces bending and perpendicular alignment. Moreover, with increasing force we observe four shape regimes, ranging from slight distortion to a state of tumbling motion that lacks a steady state. We also identify the appearance of marginally stable structures. Both the instability of these shapes and the observed alignment can be explained by the combined action of induced bending and non-local hydrodynamic interactions. Most of these effects should be experimentally relevant for stiff micro-filaments, such as microtubules.Comment: three figures. To appear in Phys Rev Let

New Perspectives on the Charging Mechanisms of Supercapacitors.

Supercapacitors (or electric double-layer capacitors) are high-power energy storage devices that store charge at the interface between porous carbon electrodes and an electrolyte solution. These devices are already employed in heavy electric vehicles and electronic devices, and can complement batteries in a more sustainable future. Their widespread application could be facilitated by the development of devices that can store more energy, without compromising their fast charging and discharging times. In situ characterization methods and computational modeling techniques have recently been developed to study the molecular mechanisms of charge storage, with the hope that better devices can be rationally designed. In this Perspective, we bring together recent findings from a range of experimental and computational studies to give a detailed picture of the charging mechanisms of supercapacitors. Nuclear magnetic resonance experiments and molecular dynamics simulations have revealed that the electrode pores contain a considerable number of ions in the absence of an applied charging potential. Experiments and computer simulations have shown that different charging mechanisms can then operate when a potential is applied, going beyond the traditional view of charging by counter-ion adsorption. It is shown that charging almost always involves ion exchange (swapping of co-ions for counter-ions), and rarely occurs by counter-ion adsorption alone. We introduce a charging mechanism parameter that quantifies the mechanism and allows comparisons between different systems. The mechanism is found to depend strongly on the polarization of the electrode, and the choice of the electrolyte and electrode materials. In light of these advances we identify new directions for supercapacitor research. Further experimental and computational work is needed to explain the factors that control supercapacitor charging mechanisms, and to establish the links between mechanisms and performance. Increased understanding and control of charging mechanisms should lead to new strategies for developing next-generation supercapacitors with improved performances.The authors acknowledge the Sims Scholarship Cambridge (A.C.F.), the School of the Physical Sciences of the University of Cambridge (via an Oppenheimer Research Fellowship, C.M.), EPSRC (via the Supergen consortium, A.C.F. and J.M.G.), and the EU ERC (via an Advanced Fellowship to C.P.G.) for funding. We thank Nicole Trease, Andrew Ilott, Phoebe Allan, Elizabeth Humphreys, Paul Bayley, Hao Wang, Patrice Simon, Wan-Yu Tsai, Yury Gogotsi, Mathieu Salanne, Benjamin Rotenberg, Alexei Kornyshev, Svyatoslav Kondrat and Volker Presser for collaboration, and stimulating discussions and insights into supercapacitors over the course of our research on this subject.This is the final version of the article. It first appeared from the American Chemical Society via https://doi.org/10.1021/jacs.6b0211

Octahedral Tilt Instability of ReO_3-type Crystals

The octahedron tilt transitions of ABX_3 perovskite-structure materials lead to an anti-polar (or antiferroelectric) arrangement of dipoles, with the low temperature structure having six sublattices polarized along various crystallographic directions. It is shown that an important mechanism driving the transition is long range dipole-dipole forces acting on both displacive and induced parts of the anion dipole. This acts in concert with short range repulsion, allowing a gain of electrostatic (Madelung) energy, both dipole-dipole and charge-charge, because the unit cell shrinks when the hard ionic spheres of the rigid octahedron tilt out of linear alignment.Comment: 4 page with 3 figures included; new version updates references and clarifies the argument