Solid-state caloric effects as intrinsic thermal responses to different physical external stimuli (magnetic-, uniaxial stress-, pressure-, and electric-fields) can achieve a higher energy efficiency compared with traditional gas compression techniques. Among these effects, magnetocaloric energy conversion is regarded as the best available alternative and has been exploited extensively for promising application scenarios in the last decades. This review systematically introduces the magnetocaloric effect and its applications, and summarizes the corresponding representative magnetocaloric materials, as well as important progress in recent years. Specifically, the review focuses on some key understandings of the magnetocaloric effect by utilizing state-of-the-art technical tools such as synchrotron X-ray, neutron scattering, muon spin spectroscopy, positron annihilation spectroscopy, high magnetic fields, etc., and highlights their importance toward advanced materials design and development. An overview of the basic principles and applications of these advanced techniques on magnetocaloric materials is provided. Finally, the challenges and perspectives on further developments in this field are discussed. Further in-depth understanding and manufacturing technology advancement combined with fast-developed artificial intelligence and machine learning are expected to advance the magnetocaloric energy conversion technology closer to real applications.

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Magnetocaloric materials undergoing reversible phase transitions are highly desirable for magnetic refrigeration applications. (Mn,Fe)₂(P,Si) alloys exhibit a giant magnetocaloric effect accompanied by a magnetoelastic transition, while the noticeable irreversibility causes drastic degradation of the magnetocaloric properties during consecutive cooling cycles. In the present work, we performed a comprehensive study on the magnetoelastic transition of the (Mn,Fe)₂(P,Si) alloys by high-resolution transmission electron microscopy, in situ field- and temperature-dependent neutron powder diffraction as well as density functional theory calculations (DFT). We found a generalized relationship between the thermal hysteresis and the transition-induced elastic strain energy for the (Mn,Fe)₂(P,Si) family. The thermal hysteresis was greatly reduced from 11 to 1 K by a mere 4 at.% substitution of Fe by Mo in the Mn_1.15Fe_0.80P_0.45Si_0.55 alloy. This reduction is found to be due to a strong reduction in the transition-induced elastic strain energy. The significantly enhanced reversibility of the magnetoelastic transition leads to a remarkable improvement of the reversible magnetocaloric properties, compared to the parent alloy. Based on the DFT calculations and the neutron diffraction experiments, we also elucidated the underlying mechanism of the tunable transition temperature for the (Mn,Fe)₂(P,Si) family, which can essentially be attributed to the strong competition between the covalent bonding and the ferromagnetic exchange coupling. The present work provides not only a new strategy to improve the reversibility of a first-order magnetic transition but also essential insight into the electron-spin-lattice coupling in giant magnetocaloric materials.

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TiNiSi-type MnCoSi-based alloys show large magnetostriction during the magnetic-field-induced metamagnetic transition. However, the high critical field required to drive the transition directly hinders their potential applications. In this work, we systematically investigate the tricritical behavior and magnetostrictive effect in substituted MnCoSi alloys. Replacing Si with Sb or In, Co with Fe or Cu, and Mn with Co, which can simultaneously reduce the critical field and the temperature of tricritical point, are explored. Among the substituted MnCoSi alloys, Mn_0.983Co_1.017Si displays a temperature of a tricritical point of 250 K and a room-temperature critical field of 0.60 T, which is the lowest up to now. Profited from these optimizations, a large reversible magnetostrictive effect under low field is successfully realized at room temperature. In a field of 1 T, the magnetostriction of Mn_0.983Co_1.017Si alloy is close to 1000 ppm. Besides, a strong relation between critical field and valence electron concentration is revealed in the transition-metal-substituted MnCoSi alloys. Our work greatly enhances the low-field magnetostrictive performance of MnCoSi-based alloys and make them be of interest in potential applications.

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We performed neutron-diffraction experiments and density functional theory calculations to study the magnetostructural coupling in MnCoGeBx (x=0, 0.01, and 0.05) alloys. By varying the amount of boron addition, we are able to freely switch the magnetostructural coupling on and off in the MnCoGe alloys. It is found that the boron addition stabilizes the high-temperature hexagonal phase due to the reduced interatomic distances and the enhanced covalent bonding. The hexagonal-orthorhombic structural transition shifts to low temperatures with the boron addition and coincides with the paramagnetic-ferromagnetic (PM-FM) transition in the MnCoGeB0.01 alloy. With a further increase in the boron addition, the structural and magnetic transitions are decoupled again. The hexagonal-orthorhombic structural transition is significantly suppressed in the MnCoGeB0.05 alloy, although subtle distortions in the hexagonal structure are evidenced by a canted spin arrangement below 75 K. The MnCoGe and MnCoGeB0.01 alloys show a collinear FM structure, having a much larger Mn moment than the MnCoGeB0.05 alloy. The relatively small Mn moment in the MnCoGeB0.05 alloy can be attributed to the shortened Mn-Mn distance and the enhanced overlap of the 3d orbitals between the neighboring Mn atoms. The uncovered relationship between the structural evolution and the sizable magnetic moment in the present work offers more insight into the magnetostructural coupling in the MnCoGe-based alloys.

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A new concept named “rotating magnetocaloric effect (RMCE)” has been proposed and attracted more attention recently. Unlike the traditional MCE that is achieved by moving the magnetic refrigerant in and out of magnetic field, RMCE can be realized by rotating the anisotropic material within the static field, thus implying the possible higher efficiency and simpler device. However, most studies on RMCE are concentrated on single crystals, which are generally more expensive and difficult to prepare in comparison with polycrystals. Therefore, it is highly desirable to search polycrystalline materials with high RMCE. Here, the textured HoNiSi polycrystal is reported to show a giant RMCE, e.g., the rotating magnetic entropy change (−ΔS_R) are 18.5 and 26.7 J/kg K and rotating adiabatic temperature change (ΔT_R) are 7.0 and 13.4 K under 2 and 5 T, respectively. This giant RMCE over a wide temperature range especially under low field suggests textured HoNiSi as promising material for practical application of rotary magnetic refrigeration. Moreover, the large magnetic anisotropy of HoNiSi is explained by the single-ion magnetic anisotropy theory, and the coherent orientation of crystallographic texture and rare-earth ion moments leads to the large RMCE in the textured HoNiSi polycrystal. This work reveals that the strongly coherent orientation of crystallographic texture and rare-earth ion moments is a key to realize large RMCE in polycrystalline materials.

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The influence of Nb substitution on the structure, magnetoelastic transition and magnetocaloric properties has been investigated for the Mn_1.1Fe_0.85-xNb_xP_0.43Si_0.57 alloys. The substitution for Fe by merely 4.7 at.% Nb (i.e. x = 0.04) significantly diminishes the thermal hysteresis from 10 to 1 K due to the reduced structural discontinuity crossing the magnetoelastic transition. This also improves the mechanical stability. The Curie temperature of the magnetoelastic transition is lowered by approximately 11.6 K per at.% of the Nb substitution, originating from the enhanced covalent bonding that favors the paramagnetic state. The giant magnetocaloric effect is still retained in the Nb-substituted alloys.

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MnMX (M = Co or Ni, X = Si or Ge) alloys with strong magnetostructural coupling exhibit giant magnetic entropy change and are currently extensively studied. However, large thermal hysteresis results in serious irreversibility of the magnetocaloric effect in this well-known system. In this work, we report a low thermal hysteresis and large reversible magnetocaloric effect in a MnNiGe-based system. The introduction of Fe into both Ni and Mn sites can establish stable magnetostructural transitions from paramagnetic hexagonal to ferromagnetic orthorhombic phases. Fascinatingly, a low thermal hysteresis of 5.2 K is achieved in Mn_0.9Fe_0.2Ni_0.9Ge alloy with a large magnetization difference of 62.1 A m²/kg between the two phases. These optimized parameters lead to a partially reversible phase transformation under a magnetic stimulus and bring about a large reversible magnetic entropy change of −18.6 Jkg⁻¹K⁻¹ under the field variation of 0–5 T, which is the largest value reported in MnMX system up to now. Moreover, this low-hysteresis magnetostructural transformation and large reversible magnetocaloric effect can be tuned by doping with Si in a wide temperature range covering room temperature. We also introduce geometrically nonlinear theory to discuss the origin of low hysteresis in MnMX alloys. A strong relation is found between thermal hysteresis and the change of c axis in the orthorhombic structure during the transition. Our work greatly develops the potential of MnMX alloys as magnetocaloric materials and is meaningful to seek or design a MnMX system with low thermal hysteresis.

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Ni-Mn-X (X = In, Sn, and Sb) based Heusler alloys show a strong potential for magnetic refrigeration owing to their large magnetocaloric effect (MCE) associated with first-order magnetostructural transition. However, the irreversibility of the MCE under low field change of 0–1 T directly hinders its application as an efficient magnetic coolant. In this work, we systematically investigate thermal and magnetic properties, crystalline structure and magnetocaloric performance in Ni51−xMn33.4In15.6Vx alloys. With the introduction of V, a stable magnetostructural transition near room temperature is observed between martensite and austenite. An extremely small hysteresis of 2.3 K is achieved for the composition x = 0.3. Due to this optimization, the magneticfield induced structural transition is partially reversible under 0–1 T cycles, resulting in a reversible MCE.
Both magnetic and calorimetric measurements consistently show that the largest value for the reversible magnetic entropy change can reach about 5.1 J kg−1 K−1 in a field change of 0–1 T. A considerable and reversible adiabatic temperature change of −1.2 K by the direct measurement is also observed under a field change of 0–1.1 T. Furthermore, the origin of this small hysteresis is discussed. Based on the lattice parameters, the transformation stretch tensor is calculated, which indicates an improved geometric compatibility between the two phases. Our work greatly improves the MCE performance of Ni-Mn-X-based alloys and make them suitable as realistic magnetic refrigeration materials.
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