The thermal stability of the high performance n-type Te-doped Mg3Sb1.5Bi0.5 system is investigated.

The application of thermoelectrics for energy harvesting depends strongly on operational reliability and it is therefore desirable to investigate the structural integrity of materials under operating conditions. We have developed an operando setup capable of simultaneously measuring X-ray scattering data and electrical resistance on pellets subjected to electrical current. Here, operando investigations of β-Zn4Sb3 are reported at current densities of 0.5, 1.14 and 2.3 A mm−2. At 0.5 A mm−2 no sample decomposition is observed, but Rietveld refinements reveal increased zinc occupancy from the anode to the cathode demonstrating zinc migration under applied current. At 1.14 A mm−2 β-Zn4Sb3 decomposes into ZnSb, but pair distribution function analysis shows that Zn2Sb2 units are preserved during the decomposition. This identifies the mobile zinc in β-Zn4Sb3 as the linkers between the Zn2Sb2 units. At 2.3 A mm−2 severe Joule heating triggers transition into the γ-Zn4Sb3 phase, which eventually decomposes into ZnSb, demonstrating Zn ion mobility also in γ-Zn4Sb3 under electrical current.

Operando characterization provides direct insight into material response under application conditions and it is essential to understand the stability limits of thermoelectric materials and their decomposition mechanisms. An operando setup capable of maintaining a thermal gradient while running DC current through a bar-shaped sample has been developed. Under operating conditions, X-ray scattering data can be measured along the sample to obtain spatially resolved structural knowledge in concert with measurement of electrical resistance and the Seebeck coefficient. Here thermoelectric β-Zn4Sb3, which is a mixed ionic–electronic conductor, is studied, and a significant temperature dependence of the Zn migration is directly observed. Measurements with the thermal gradient applied either along or opposite to the DC current establish that the ion migration is an electrochemical effect rather than a thermodiffusion. Consideration of only the applied critical voltage or current density is insufficient for deducing the stability limits and structural integrity of materials with temperature-dependent ion mobility. The present operando setup is not limited to studies of thermoelectric materials, and it also lends itself to studies of, for example, ion diffusion in solid-state electrolytes or structural transformations in solid-state reactions.

N-type Mg 3 (Sb,Bi) 2 compounds have recently been demonstrated as promising low-cost efficient thermoelectric materials in low and intermediate temperature ranges; however, the thermal stability of this type of material still poses a great challenge for practical applications. In this work, we conduct a systematic investigation of the thermal stability of several highperforming n-type Mg 3 (Sb,Bi) 2 -based thermoelectric materials in both bulk and powdered forms using X-ray and neutron diffraction. It is found that the bulk sample exhibits a much slower degradation rate based on the evolution of the secondary Bi/Sb phase in comparison with the powdered sample, revealing a clear kinetic effect. Moreover, the surface of the bulk sample will gradually become Mg-poor or Bi-rich even at room temperature when exposed to air for a long time, highlighting the importance of surface encapsulation for applications. An underlying mechanism based on the Mg loss/migration is proposed to account for the property degradation. Importantly, to address the property degradation, we discuss possible solutions and propose Mg-vapor annealing as an effective approach to enhance thermal stability by suppressing the Mg loss/migration through saturating grains and grain boundaries with elemental Mg. We expect a combination of the Mg-vapor annealing and surface coating to further improve the long-term thermal stability. This work sheds light on the strategies for enhancing the long-term stability of n-type Mg 3 Sb 2 -based thermoelectrics for practical applications.

Electron density determination based on structure factors obtained through powder X‐ray diffraction has so far been limited to high‐symmetry inorganic solids. This limit is challenged by determining high‐quality structure factors for crystalline urea using a bespoke vacuum diffractometer with imaging plates. This allows the collection of data of sufficient quality to model the electron density of a molecular system using the multipole method. The structure factors, refined parameters as well as chemical bonding features are compared with results from the high‐quality synchrotron single‐crystal study by Birkedal et al. [Acta Cryst. (2004), A60, 371–381] demonstrating that powder X‐ray diffraction potentially provides a viable alternative for electron density determination in simple molecular crystals where high‐quality single crystals are not available.