Search for: All records

The layered transition metal chalcogenides MCrX₂ (M = Ag, Cu; X = S, Se, Te) are of interest for energy storage because chemically Li-substituted analogs were reported as superionic Li⁺ conductors. The coexistence of fast ion transport and reducible transition metal and chalcogen elements suggests that this family may offer multifunctional capability for electrochemical storage. Here, we investigate the electrochemical reduction of AgCrSe₂ and CuCrSe₂ in non-aqueous Li- and Na-ion electrolytes using electrochemical measurements coupled with ex situ characterization (scanning electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy). Both compounds delivered high initial specific capacities (~ 560 mAh/g), corresponding to 6.64 and 5.73 Li⁺/e^- per formula unit for AgCrSe₂ and CuCrSe₂, respectively. We attribute this difference to distinct reduction pathways: 1) Li⁺ intercalation to form LiCrSe₂ and extruded Ag or Cu, 2) conversion of LiCrSe₂ to Li₂Se, and 3) formation of an Ag-Li alloy at the lowest potential, operative only in AgCrSe₂. Consistent with this proposed mechanism, step 3 was absent during reduction of AgCrSe₂ in a Na-ion electrolyte since Ag does not alloy with Na. These results demonstrate the complex reduction chemistry of MCrX₂ in the presence of alkali ions, providing insights into the use of MCrX₂ materials as alkali ion superionic conductors or high capacity electrodes for lithium or sodium-ion type batteries. 

Abstract Superionic conductors, includingACrX₂(A=Ag, Cu; X = S, Se) compounds, have attracted attention due to their low lattice thermal conductivity and high ionic conductivity. These properties are driven by structural characteristics such as anharmonicity, soft bonding, and disorder, which enhance both fast ion transport and thermal resistance. In the present study, we investigate the impact of various factors (e.g.A-site disorder, microstructure, speed of sound and chemical composition) on the thermal conductivity of the compounds CuCrS₂, CuCrSe₂, AgCrS₂and AgCrSe₂. The samples were synthesized using solid state reaction, ball milling and subsequent spark plasma sintering, and thermal diffusivity, electrical resistivity, Hall coefficients and Seebeck coefficients were measured as a function of temperature. The selenides were found to behave as degenerate semiconductors, with reasonable thermoelectric figure of merit (up to 0.79 in CuCrSe₂), while the sulfides behaved as non-degenerate semiconductors with high electrical resistivity. At room temperature, all samples are in the ordered phase and show low lattice thermal conductivity ranging from 0.60 W m⁻¹-K in AgCrSe₂to 1.1 W m⁻¹-K in CuCrSe₂. Little reduction in lattice thermal conductivity was observed in the high-temperature phase, despite the increased disorder on the cation site and the onset of superionic conductivity. This suggests that the low lattice thermal conductivity inACrX₂compounds is an inherent property of the crystal structure, caused by anharmonic bonding and diffuson dominated transport. 

Abstract Bandstructure engineering is a key route for thermoelectric performance enhancement. Here, 20–50% Seebeck (S) enhancement is reported for XNiCu_ySn half‐Heusler samples based onX= Ti. This novel electronic effect is attributed to the emergence of impurity bands of finite extent, due to the Cu dopants. Depending on the dispersion, extent, and offset with respect to the parent material, these bands are shown to enhanceSto different degrees. Experimentally, this effect is controllable by the Ti content of the samples, with the addition of Zr/Hf gradually removing the enhancement. At the same time, the mobility remains largely intact, enabling power factors ≥3 mW m⁻¹K⁻²near room temperature, increasing to ≥5 mW m⁻¹K⁻²at high temperature. Combined with reduced thermal conductivity due to the Cu interstitials, this enables high averagezT= 0.67–0.72 between 320 and 793 K for XNiCu_ySn compositions with ≥70% Ti. This work reveals the existence of a new route for electronic performance enhancement in n‐type XNiSn materials that are normally limited by their single carrier pocket. In principle, impurity bands can be applied to other materials and provide a new direction for further development. 

Aliovalent substitutions lead to bond disorder and low lattice thermal conductivities in half-Heusler thermoelectrics. 

Abstract While ∼30% of materials are reported to be topological, topological insulators are rare. Magnetic topological insulators (MTI) are even harder to find. Identifying crystallographic features that can host the coexistence of a topological insulating phase with magnetic order is vital for finding intrinsic MTI materials. Thus far, most materials that are investigated for the determination of an MTI are some combination of known topological insulators with a magnetic ion such as MnBi₂Te₄. Motivated by the recent success of EuIn₂As₂, the role of chemical pressure on topologically trivial insulator is investigated, Eu₅In₂Sb₆via Ga substitution. Eu₅Ga₂Sb₆is predicted to be topological but is synthetically difficult to stabilize. The intermediate compositions between Eu₅In₂Sb₆and Eu₅Ga₂Sb₆are observed through theoretical works to explore a topological phase transition and band inversion mechanism. The band inversion mechanism is attributed to changes in Eu–Sb hybridization as Ga is substituted for In due to chemical pressure. Eu₅In_4/3Ga_2/3Sb₆is also synthesized, the highest Ga concentration in Eu₅In_2‐xGa_xSb₆, and report the thermodynamic, magnetic, transport, and Hall properties. Overall, the work paints a picture of a possible MTI via band engineering and explains why Eu‐based Zintl compounds are suitable for the co‐existence of magnetism and topology.