Magnetic refrigeration material ETMNO and preparation method and application thereof

Abstract

The invention discloses a magnetic refrigeration material ETMNO and a preparation method and application thereof, and belongs to the technical field of magnetic refrigeration, the chemical general formula of the magnetic refrigeration material ETMNO is Eu64 (Ti64-x-yMxNy) O192, wherein M is any one of Sc, Nb, Mo, Ag, Ta or W, and N is any one of Cr, Mn, Fe, Cu, Zn, B, Si, Ga, Ge or Zr; wherein 1 < = x < = 16, 1 < = y < = 16; according to the magnetic refrigeration material ETMNO provided by the technical scheme, the maximum magnetic entropy change of the magnetic refrigeration material ETMNO under the magnetic field change of 0-1 T and 0-0.5 T can reach 21.6 J.kg <-1 > K <-1 > and 12.8 J.kg <-1 > K <-1 > respectively, the magnetic refrigeration capacity can reach 97.0 J.kg <-1 > and 42.1 J.kg <-1 > respectively, and the magnetic refrigeration material has excellent magnetocaloric performance in a liquid helium temperature zone, can be applied to the refrigeration technology in the liquid helium temperature zone, and has good application prospects. The preparation method of the magnetic refrigeration material ETMNO provided by the invention is simple in process, safe and environment-friendly, and can be applied to industrial production.

Description

technical field [0001] The invention belongs to the technical field of magnetic refrigeration, in particular to a magnetic refrigeration material ETMNO and its preparation method and application. Background technique [0002] Since the 20th century, cryogenic refrigeration technology has achieved unprecedented development and application, and has become one of the key supporting technologies for the development of modern science and technology. Among them, liquid helium temperature zone refrigeration is an indispensable key link to realize extremely low temperature refrigeration, and plays an important role in the fields of low temperature physics, low temperature superconductivity, aerospace and military industry. At present, the mainstream way to obtain the temperature of liquid helium is to use the Gifford-McMahon (GM) refrigerator, but its refrigeration efficiency is only about 1% of the Carnot cycle efficiency. Therefore, how to effectively improve the refrigeration ef...

AI Technical Summary

Problems solved by technology

In recent years, materials with low magnetic field and large magnetocaloric effect have become a research hotspot and development trend in the field of magnetic refrigeration materials; many rare earth-based alloy materials, such as ErMn 2 Si 2 , ErNiBC, TmCuAl and TmCoSi, etc., have been found to have a large magnetocaloric effect in the liquid helium temperature region; however, rare earth-based alloy materials usually have the following characteristics: ① the cost is high; ② they are mostly prepared by arc melting method, which requires high vacuum. High equipment requirements; ③The product is easy to oxidize and difficult to store; ④Usually it needs to go through repeated smelting and long-time annealing to obtain the pure phase, which consumes a lot of energy; thus, its large-scale application is greatly restricted; Gd( Oh) 3 , Gd(OH)CO 3 and Gd(HCOO) 3 Single crystals have a strong magnetocaloric effect near the temperature of liquid helium, and the maximum magnetic entropy changes under 0-1T magnetic field changes are 9.0J kg -1 ·K -1 , 12.6J·kg -1 ·K -1 and 12.4J kg -1 ·K -1 , but the preparation process of single crystal is complicated, the cycle is long, and it is difficult to prepare on a large scale, which limits its practical application

[0005] CN107910151B discloses a non-rare earth magnetic refrigeration material KBBFO and its preparation method. The material is prepared by a hydrothermal method, which has the advantages of simple process and short cycle, but its maximum magnetic entropy change under the 0-1T magnetic field change is only about 0.23J·kg -1 ·K -1 ; CN111072063A discloses a perovskite rare earth metal oxide low temperature magnetic refrigeration material EuTi 1-x Al x o 3 And its preparation method, its magnetic entropy change value under the 0-1T magnetic field change is 11.6-15.6J·kg -1 ·K -1 , the magnetic refrigeration capacity is 48~58.2J·kg -1 , showing good magnetocaloric properties near the phase transition temperature; however, a large amount of chemicals such as nitric acid, tetrabutyl titanate, aluminum chloride and ethylene glycol are used in the preparation process of the material, and these chemicals The product will produce a large amount of toxic and harmful gases such as nitrogen dioxide and hydrogen chloride in the subsequent sintering process, which will not only endanger the health of the workers, but also cause serious environmental pollution, which is not suitable for industrial production

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