Vanadium oxides have been recognized to be among the most promising positive electrode materials for aqueous zinc metal batteries (AZMBs). However, their underlying intercalation mechanisms are still vigorously debated. To shed light on the intercalation mechanisms, high-performance δ-V₂O₅ is investigated as a model compound. Its structural and electrochemical behaviors in the designed cells with three different electrolytes, i.e., 3 m Zn(CF₃SO₃)₂/water, 0.01 M H₂SO₄/water, and 1 M Zn(CF₃SO₃)₂/acetonitrile, demonstrate that the conventional structural and elemental characterization methods cannot adequately clarify the separate roles of H⁺ and Zn²⁺ intercalations in the Zn(CF₃SO₃)₂/water electrolyte. Thus, an operando pH determination method is developed and used toward Zn/δ-V₂O₅ AZMBs. This method indicates the intercalation of both H⁺ and Zn²⁺ into δ-V₂O₅ and uncovers an unusual H⁺/Zn²⁺-exchange intercalation–deintercalation mechanism. Density functional theory calculations further reveal that the H⁺/Zn²⁺ intercalation chemistry is a consequence of the variation of the electrochemical potential of Zn²⁺ and H⁺ during the electrochemical intercalation/release.

Engineering lattice thermal conductivity requires to control the heat carried by atomic vibration waves, the phonons. The key parameter for quantifying it is the phonon lifetime, limiting the travelling distance, whose determination is however at the limits of instrumental capabilities. Here, we show the achievement of a direct quantitative measurement of phonon lifetimes in a single crystal of the clathrate Ba_7.81Ge_40.67Au_5.33, renowned for its puzzling ‘glass-like’ thermal conductivity. Surprisingly, thermal transport is dominated by acoustic phonons with long lifetimes, travelling over distances of 10 to 100 nm as their wave-vector goes from 0.3 to 0.1 Å⁻¹. Considering only low-energy acoustic phonons, and their observed lifetime, leads to a calculated thermal conductivity very close to the experimental one. Our results challenge the current picture of thermal transport in clathrates, underlining the inability of state-of-the-art simulations to reproduce the experimental data, thus representing a crucial experimental input for theoretical developments.

Perfectly crystalline solids are excellent heat conductors. Prominent counterexamples are intermetallic clathrates, guest-host systems with a high potential for thermoelectric applications due to their ultralow thermal conductivities. Our combined experimental and theoretical investigation of the lattice dynamics of a particularly simple binary representative, ${\mathrm{Ba}}_8{\mathrm{Si}}_{46}$, identifies the mechanism responsible for the reduction of lattice thermal conductivity intrinsic to the perfect crystal structure. Above a critical wave vector, the purely harmonic guest-host interaction leads to a drastic transfer of spectral weight to the guest atoms, corresponding to a localization of the propagative phonons.

One of the key requirements for good thermoelectric materials is a low lattice thermal conductivity. Here we present a combined neutron scattering and theoretical investigation of the lattice dynamics in the type I clathrate system Ba-Ge-Ni, which fulfills this requirement. We observe a strong hybridization between phonons of the Ba guest atoms and acoustic phonons of the Ge-Ni host structure over a wide region of the Brillouin zone, which is in contrast with the frequently adopted picture of isolated Ba atoms in Ge-Ni host cages. It occurs without a strong decrease of the acoustic phonon lifetime, which contradicts the usual assumption of strong anharmonic phonon\char21{}phonon scattering processes. Within the framework of ab initio density-functional theory calculations we interpret these hybridizations as a series of anticrossings which act as a low-pass filter, preventing the propagation of acoustic phonons. To highlight the effect of such a phononic low-pass filter on the thermal transport, we compute the contribution of acoustic phonons to the thermal conductivity of Ba8Ge40Ni6 and compare it to those of pure Ge and a Ge46 empty-cage model system.