Magnetocaloric effect: From materials research to refrigeration devices

Spintronics is a multidisciplinary field involving physics, chemistry, and engineering, and is a new research area for solid-state scientists. A variety of new materials must be found to satisfy different demands. The search for ferromagnetic semiconductors and stable half-metallic ferromagnets with Curie temperatures higher than room temperature remains a priority for solid-state chemistry. A general understanding of structure-property relationships is a necessary prerequisite for the design of new materials. In this Review, the most important developments in the field of spintronics are described from the point of view of materials science.

Spintronics: a challenge for materials science and solid-state chemistry.

Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B-O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co-O bond and the concentration of oxygen vacancies are controlled through Sr(2+) substitution into La(1-x)Sr(x)CoO(3-δ) . We attempt to rationalize the high activities of La(1-x)Sr(x)CoO(3-δ) through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.

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Water electrolysis on La(1-x)Sr(x)CoO(3-δ) perovskite electrocatalysts.

In this work, results of {\it ab-initio} band structure calculations for $A_2BC$ Heusler compounds that have $A$ and $B$ sites occupied by transition metals and $C$ by a main group element are presented. This class of materials includes some interesting half-metallic and ferromagnetic properties. The calculations have been performed in order to understand the properties of the minority band gap and the peculiar magnetic behavior found in these materials. Among the interesting aspects of the electronic structure of the materials are the contributions from both $A$ and $B$ atoms to states near the Fermi energy and to the total magnetic moment. The magnitude of the total magnetic moment, which depends as well on the kind of $C$ atoms, shows a trend consistent with the Slater-Pauling type behavior in several classes of these compounds. The localized moment in these magnetic compounds resides at the $B$ site. Other than in the classical Cu$_2$-based Heusler compounds, the $A$ atoms in Co$_2$, Fe$_2$, and Mn$_2$ based compounds may contribute pronounced to the total magnetic moment.

Calculated electronic and magnetic properties of the half-metallic, transition metal based Heusler compounds

In this paper, results of ab initio band structure calculations for A2BC Heusler compounds that have A and B sites occupied by transition metals and C by a main group element are presented. This class of materials includes some interesting half-metallic and ferromagnetic properties. The calculations have been performed in order to understand the properties of the minority band gap, the peculiar transport properties and magnetic behaviour found in these materials. Among the interesting aspects of the electronic structure of the materials are the contributions from both A and B atoms to the total magnetic moment. The magnitude of the total magnetic moment shows a trend consistent with the Slater–Pauling type behaviour in several classes of these compounds. The total magnetic moment also depends on the kind of C atoms although they do not directly contribute to it. In Co2 compounds, a change of the C element changes the contribution of the t2g states to the moment at the Co sites. The localized moment in these magnetic compounds resides at the B site. Other than in the classical Cu2-based Heusler compounds, the A atoms in Co2, Fe2 and Mn2-based compounds may contribute significantly to the total magnetic moment. It is shown that the inclusion of electron–electron correlation in the form of LDA + U calculations helps to understand the magnetic properties of those compounds that already exhibit a minority gap in calculations where it is neglected. Besides the large group of Co2 compounds, half-metallic ferromagnetism was here found only in such compounds that contain Mn.

https://iopscience.iop.org/article/10.1088/0022-3727/40/6/S01/pdf

Effect of Eu substitution on the crystal structure and multiferroic properties of BiFeO3

Comparison of the high temperature thermoelectric properties for Ag-doped and Ag-added Ca3Co4O9

We report a systematical investigation on the high temperature thermoelectric response of Ca1−xRxMnO3 (R = rare-earth) perovskites in the electron-doped range. The results reveal that electron concentration is the dominant factor for the high temperature electrical transport properties whereas the weight and size of R ions dominate the thermal transport properties. As the doping level varies, the best thermoelectric performance is observed at the relative electron concentration around 0.1. However, in the case of a fixed electron concentration, structural distortions become important since bandwidth has an observable influence on resistivity. By combining the three factors, electron concentration, crystal structure, and the weight/size of R ions, the largest thermoelectric figure of merit ZT for Ca1−xRxMnO3 reaches 0.2 at 1000 K. But this ZT value is still too far from the application criterion (ZT > 1). Using the dynamical mean field theory, we demonstrate that a ZT value larger than one in electron-dope...

High Temperature Thermoelectric Response of Electron-Doped CaMnO3

We report the strongly correlated, electrical transport, magnetic, and thermoelectric properties of a series of Fe, Mn, and Cu doped Ca3Co4O9. The results indicate that Fe/Mn substitutes for Co in CoO2 layers whereas Cu substitutes for Co in Ca2CoO3 layers. Because of the different doping sites, the electronic correlations increase remarkably in Fe and Mn doped series while remaining unchanged in Cu doped series. Correspondingly, the transport mechanism, magnetic properties, and some characteristic parameters along with transition temperatures all exhibit two distinct evolutions for Fe/Mn doping and Cu doping. The thermoelectric characteristics are improved in each series. Nevertheless, the improvement of thermoelectric performance is most significant in Fe doped samples due to the unexpected changes in thermopower and resistivity. The unusual thermopower behavior can be well described by the variations of electronic correlation. Possible approaches for further improvement of the thermoelectric performanc...

Strongly Correlated Properties and Enhanced Thermoelectric Response in Ca3Co4−xMxO9 (M = Fe, Mn, and Cu)†

Perovskite YFe0.5Cr0.5O3 exhibits magnetization reversal at low applied fields due to the competition between the single ion magnetic anisotropy and the antisymmetric Dzyaloshinsky–Moriya interaction. Below a compensation temperature (Tcomp), a tunable bipolar switching of magnetization is demonstrated by changing the magnitude of the field while keeping it in the same direction. The present compound also displays both normal and inverse magnetocaloric effects above and below 260 K, respectively. These phenomena coexisting in a single magnetic system can be tuned in a predictable manner and have potential applications in electromagnetic devices.

Yu Sui

Papers

Effect of Eu substitution on the crystal structure and multiferroic properties of BiFeO3

Comparison of the high temperature thermoelectric properties for Ag-doped and Ag-added Ca3Co4O9

High Temperature Thermoelectric Response of Electron-Doped CaMnO3

Strongly Correlated Properties and Enhanced Thermoelectric Response in Ca3Co4−xMxO9 (M = Fe, Mn, and Cu)†

Temperature- and magnetic-field-induced magnetization reversal in perovskite YFe0.5Cr0.5O3