Lithium oxides LiRO2 (R = rare earth elements) with negative thermal expansion behavior and inverse barocaloric effect

Abstract

Negative thermal expansion (NTE) defies the conventional wisdom of lattice dynamics and offers a novel way to control the expansion coefficient and address some challenges in modern science and technology. From an application standpoint, materials exhibiting NTE across a broad temperature range, including room temperature, are highly sought after. In this work, we propose the multi-doping strategy and prepared a series of rare-earth-based lithium oxides featuring negative thermal expansion, with the objective of adjusting their temperature range. The phase transition temperatures of these materials range from 202 K to 467 K, demonstrating a linear correlation with the average ionic radius of the rare-earth elements. By capitalizing on the synergistic effects of four rare-earth elements, we expand the full width at half maximum of the thermal expansion peak in Li(ErYHoDy)0.25O2 from 1.6 K to 14.5 K, a notable improvement of nearly tenfold is achieved. Additionally, we investigate the low-temperature magnetocaloric effects and inverse barocaloric effects within these rare-earth-based lithium oxides. Temperature- and pressure-dependent Raman scattering measurements indicate that the phase transitions and the barocaloric effects are associated with the stretching mode of the Li–O bond and the vibrational mode of the YO6 octahedron.

Keywords

• Negative thermal expansion
• Widening operating-temperature window
• Inverse barocaloric effect
• Rare earth elements doping