CN113035480A - Magnetic refrigeration material and preparation method and application thereof - Google Patents
Magnetic refrigeration material and preparation method and application thereof Download PDFInfo
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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Abstract
The invention provides a magnetic refrigeration material, a preparation method and application thereof, wherein the magnetic refrigeration material comprises LiGdF4The magnetic refrigeration material has strong magnetocaloric effect at low temperature, and the maximum magnetic entropy change under the magnetic field change of 0-5T at the temperature of 2.5K is less than or equal to 58 J.kg‑1·K‑1It is a magnetic refrigeration material with excellent performance. The magnetic refrigeration material consists of LiF and GdF3The material is prepared by solid-phase reaction, does not need to use harmful substances such as acid or alkali which pollute the environment, has simple preparation process and shorter period, is suitable for large-scale industrial production, and has wide application prospect in the fields of low-temperature physics, space exploration, aerospace and the like.
Description
Technical Field
The invention relates to the technical field of magnetic refrigeration materials, in particular to a magnetic refrigeration material and a preparation method and application thereof.
Background
When an external magnetic field is changed, a ferromagnetic or paramagnetic material is accompanied by the change of the order degree of magnetic moments, that is, the magnetic entropy changes, so that the material itself absorbs or releases heat, which is called a magnetocaloric effect. When no external magnetic field exists, the directions of magnetic moments in the material are disordered, and the magnetic entropy of the material is larger; when an external magnetic field is applied, the orientations of the magnetic moments in the material gradually tend to be consistent, and the magnetic entropy of the material is smaller. One class of materials having a magnetocaloric effect is called magnetic refrigeration materials, and magnetic refrigeration technology is a new technology for achieving refrigeration using the magnetocaloric effect of materials.
In the process of excitation, the magnetic moment of the magnetic material is changed from disorder to order along the direction of a magnetic field, the magnetic entropy is reduced, and the thermodynamic principle shows that the magnetic working medium releases heat outwards at the moment; in the demagnetizing process, the magnetic moment of the magnetic material is changed from order to disorder along the magnetic field direction, the magnetic entropy is increased, and at the moment, the magnetic working medium absorbs heat from the outside. Under the adiabatic condition, the magnetic working medium does not exchange heat with the external environment, and in the excitation and demagnetization processes, the magnetic field applies work to the material to change the internal energy of the material, so that the temperature of the material changes. The above is the basic principle of the magnetic refrigeration technology.
Compared with the traditional gas compression type refrigeration technology, the magnetic refrigeration technology has the advantages of environmental protection, energy conservation, high efficiency, stability, reliability and the like. Firstly, what magnetic refrigeration technology adopted is solid state refrigeration working medium, need not to use poisonous and harmful such as freon, easily leak, combustible gas, can not produce destruction and greenhouse effect scheduling problem to the ozone layer, have green, safe, the characteristics of environmental protection. And secondly, the thermodynamic process of the magnetic refrigeration generating the magnetocaloric effect is highly reversible, the intrinsic thermodynamic efficiency can reach the Carnot efficiency theoretically, the actual efficiency can reach 60-70% of the Carnot cycle efficiency, the energy is saved, the efficiency is high, and the advantages are obvious. Thirdly, the magnetic refrigeration does not need a gas compressor, and the magnetic refrigeration has the advantages of small vibration and noise, long service life, good stability and high reliability.
The magnetic refrigeration material is the basis of the magnetic refrigeration technology, and the development of the giant magnetocaloric effect material which has large magnetic entropy change, high refrigeration capacity, stability, reliability and easy mass production is the key for developing the magnetic refrigeration technology. In recent years, rare earth metal compounds have a strong magnetocaloric effect, are simple in preparation process, are suitable for large-scale production, and have become one of the focuses of research in the field of magnetic refrigeration materials. The development of a rare earth metal compound material system with giant magnetocaloric effect and the promotion of the industrial application of the magnetic refrigeration technology based on the rare earth metal compound material system are beneficial to the development of the low-temperature physics, space exploration, aerospace and other technologies in China, and are also beneficial to promoting the high-valued utilization of rare earth resources in China and improving the competitiveness and technical level of the rare earth industry in China.
CN104559944A discloses a magnetic refrigeration material containing rare earth hydroxide and a preparation method thereof, wherein the composition formula of the magnetic refrigeration material is Gd (OH)8/3Cl1/3The maximum magnetic entropy of the magnetic material under the magnetic field change of 0-5T is about 3K and is 48 J.kg-1·K-1And the maximum magnetic entropy under the change of the magnetic field of 0-7T is up to 60 J.kg-1·K-1And has high low-temperature magnetocaloric effect. However, a large amount of hydrochloric acid and sodium hydroxide are needed in the preparation process of the magnetic refrigeration material, the use of the strong acid and the strong base inevitably causes pollution to the environment, large-scale production is difficult to realize, the product can be obtained only by hydrothermal reaction at a high temperature of 200 ℃ for 2 days, the energy consumption is high, the preparation period is long, and the preparation method is not suitable for industrial production.
CN105714378B discloses a crystalline material, whose molecular formula is: gd (Gd)2Cu(SO4)2(OH)4The maximum magnetic entropy of the magnetic material under the change of a 0-8T magnetic field is 45.5 J.kg-1·K-1And has higher magnetocaloric effect. However, the crystal preparation needs to be crystallized at 200-230 ℃ for 3-5 days, and then cooled to room temperature for 3-5 days, so that the product can be obtained, the preparation period is too long, the energy consumption is too large, and the crystal preparation is not suitable for large-scale industrial production.
CN108840364B discloses an inorganic gadolinium-based complex crystal and a preparation method thereof, wherein the maximum magnetic entropy of the crystal is 53.49 J.kg under the condition of 0-7T magnetic field change at the temperature of 2K-1·K-1The maximum magnetic entropy change under the change of 0-5T magnetic field is about 49 J.kg-1·K-1It is a better magnetic refrigeration material. However, the preparation process of the crystal also has the problems of long period and high energy consumption, and the crystal with good crystallinity can be obtained only by crystallizing for 7 days at 180 ℃ in a stainless steel high-pressure reaction vessel with a polytetrafluoroethylene reaction kettle.
Therefore, there is a need to develop a magnetic refrigeration material with simple process, short preparation period and excellent magnetic refrigeration effect.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a magnetic refrigeration material, a preparation method and application thereof, wherein the magnetic refrigeration material comprises LiGdF4The preparation method of the magnetic refrigeration material comprises the steps of mixing and placing raw materials in a first container, then placing the raw materials in a second container, and carrying out a solid-phase reaction process of sintering.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a magnetic refrigeration material comprising LiGdF4。
Preferably, the maximum magnetic entropy change of the magnetic refrigeration material is less than or equal to 58J-kg under the condition of 0-5T magnetic field change at the temperature of 2.5K-1·K-1For example, 58 J.kg may be used-1·K-1、57J·kg-1·K-1Or 56 J.kg-1·K-1And the like.
Preferably, the maximum magnetic entropy change of the magnetic refrigeration material is less than or equal to 29J-kg under the condition of 0-2T magnetic field change at the temperature of 2.5K-1·K-1For example, it may be 29 J.kg-1·K-1、28J·kg-1·K-1Or 27 J.kg-1·K-1And the like.
Preferably, the maximum magnetic entropy change of the magnetic refrigeration material under the condition of 0-1.5T magnetic field change at the temperature of 2.5K is less than or equal to 20J-kg-1·K-1For example, it may be 20 J.kg-1·K-1、19J·kg-1·K-1Or 18 J.kg-1·K-1And the like.
The magnetic refrigeration material comprises LiGdF4Is a material with giant magnetocaloric effect, and the magnetic refrigeration material is made of LiF and GdF3The polycrystalline material formed by the solid-phase reaction has weak dipole and exchange effect in the material and cross-induced quadrupole effect, so that the polycrystalline material has good magnetocaloric property at low temperature (2.5K), and is superior to the materials in the prior art and most magnetic refrigeration materials (such as ErMn)2Si2HoCuSi, TmCuAl, etc.), can realize a good magnetic refrigeration effect, and is a magnetic refrigeration material with excellent performance.
Preferably, the magnetic refrigeration material comprises pure-phase LiGdF4。
"including" in the present invention may be replaced with "consisting of …".
Preferably, the magnetic refrigeration material is tetragonal.
Preferably, the space group of the magnetic refrigeration material is I41/a。
In a second aspect, the present invention provides a method for preparing the magnetic refrigeration material according to the first aspect, wherein the method comprises the following steps:
(1) mixing LiF and GdF3Obtaining a mixture;
(2) placing the mixture of step (1) in a first container, and sealing the first container;
(3) putting the first container obtained in the step (2) into a second container, spreading carbon powder outside the first container, and sealing the second container;
(4) and (4) sintering the second container in the step (3) to obtain the magnetic refrigeration material.
The invention combines LiF and GdF3After the mixture is fully mixed, the mixture is placed in a first container, a cover of the first container is covered, then the first container is placed in a second container, carbon powder is fully paved outside the first container, and the cover of the second container is covered, so that the volatilization of LiF can be reduced, the influence of external atmosphere on the mixture can be reduced, the smooth proceeding of solid phase reaction is facilitated, and the phase purity of the magnetic refrigeration material is improved; and finally, sintering to obtain the magnetic refrigeration material with strong magnetocaloric effect.
Preferably, the LiF and GdF of step (1)3The ratio of the amounts of the components (1) to (2): 1 may be, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2: 1.
Preferably, the LiF and GdF3The amount ratio of the substance(s) is (1.2-1.8): 1.
Preferably, the LiF and GdF3The amount ratio of the substance(s) is (1.6-1.8): 1.
Preferably, the mixing is done in a mortar, ball mill or blender.
The mixing in the invention can be grinding by a mortar, ball milling by a ball mill, or LiF and GdF3Mixing by a mixer within the particle size range of the mixture. The purpose is to mix LiF and GdF3Fully contacting, uniformly mixing and achieving the required particle size.
Preferably, the mixture has an average particle size of 100 μm or less, and may be, for example, 100 μm, 95 μm, 90 μm, 85 μm, 80 μm, 75 μm, 70 μm, 65 μm, 60 μm, 55 μm, 50 μm, 45 μm, 40 μm, 35 μm, 30 μm, 20 μm, 10 μm or the like.
Preferably, the first container of step (2) comprises a first crucible.
Preferably, the material of the first crucible comprises corundum, quartz, graphite, zirconia, boron nitride, silicon carbide or silicon nitride.
Preferably, the second container of step (3) comprises a second crucible.
Preferably, the material of the second crucible comprises corundum, graphite, zirconia, silicon carbide or silicon nitride.
Preferably, the carbon powder comprises any one or a combination of at least two of graphite, activated carbon, coke, or carbon black, wherein a typical but non-limiting combination is: a combination of graphite and activated carbon, a combination of activated carbon and coke, a combination of coke and carbon black, and a combination of activated carbon, coke and carbon black.
Preferably, the carbon powder has an average particle size of 500 μm or less, and may be, for example, 500 μm, 450 μm, 400 μm, 350 μm, 300 μm, 250 μm, 200 μm, 180 μm, 160 μm, 140 μm, 120 μm, or the like.
Preferably, the sintering of step (4) is performed in a sintering furnace.
Preferably, the sintering furnace comprises a muffle furnace, a tube furnace or a vacuum furnace.
Preferably, the sintering temperature is 800-1200 ℃, for example, 800 ℃, 840 ℃, 880 ℃, 920 ℃, 960 ℃, 1000 ℃, 1040 ℃, 1080 ℃, 1120 ℃, 1160 ℃ or 1200 ℃.
The sintering temperature is 800-1200 ℃, the temperature can effectively promote the mass transfer process of substances, ensure the smooth proceeding of solid phase reaction, and avoid the problems that LiF is excessively volatilized due to overhigh temperature, the control difficulty of the reaction process is increased, so that the phase composition and the performance of the material are influenced, and the energy consumption is favorably reduced.
Preferably, the sintering time is 10-60 min, for example, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60 min.
The sintering time is 10-60 min, and within the time range, the mass transfer process can be ensured, so that the solid-phase reaction is fully performed, the phenomenon that the phase purity of the material is influenced by the excessive volatilization of LiF due to long-time heating can be prevented, and the production efficiency can be improved.
Preferably, the sintering is performed under an air atmosphere or an inert atmosphere.
Preferably, the inert atmosphere comprises argon and/or nitrogen.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing LiF and GdF according to the mass ratio of (1-2) to 13To obtain a mixture with the average grain diameter less than or equal to 100 mu m;
(2) placing the mixture of step (1) in a first container, and sealing the first container;
(3) putting the first container in the step (2) into a second container, fully spreading carbon powder with the average particle size of less than or equal to 500 mu m outside the first container, and sealing the second container;
(4) and (4) placing the second container in the step (3) into a sintering furnace, and sintering at the temperature of 800-1200 ℃ for 10-60 min to obtain the magnetic refrigeration material.
In a third aspect, the invention provides a magnetic refrigeration material according to the first aspect for use in the fields of low-temperature physics, space exploration and aerospace.
The magnetic refrigeration material has strong low-temperature magnetocaloric effect, and the maximum magnetic entropy change under the magnetic field change of 0-5T at the temperature of 2.5K is less than or equal to 58 J.kg-1·K-1The maximum magnetic entropy changes under the magnetic field changes of 0-2T and 0-1.5T are respectively less than or equal to 29 J.kg-1·K-1And less than or equal to 20 J.kg-1·K-1The material is a giant magnetocaloric effect material, can be expected to be used as a refrigeration working medium in a magnetic refrigerator, can achieve good refrigeration effect, adopts a solid refrigeration working medium, does not produce harmful gas, is green and environment-friendly, has high thermodynamic efficiency, is energy-saving and efficient, has stable performance and long service life, can be widely applied to the fields of low-temperature physics, space exploration and aerospace, and is beneficial to promoting the high-valued utilization of rare earth resources.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention provides a magnetic refrigeration material, which comprises LiGdF4The magnetic refrigeration material has a giant magnetocaloric effect, and the maximum magnetic entropy change under the magnetic field change of 0-5T at the temperature of 2.5K is less than or equal to 58 J.kg-1·K-1And the maximum magnetic entropy changes under the magnetic field changes of 0-2T and 0-1.5T are respectively less than or equal to 29 J.kg-1·K-1And less than or equal to 20 J.kg-1·K-1Is superior to the prior art and most magnetic refrigeration materials (such asErMn2Si2HoCuSi, TmCuAl, etc.), which is a low-temperature magnetic refrigeration material with excellent performance;
(2) according to the preparation method of the magnetic refrigeration material, the raw materials are mixed and then placed in the first container, and then placed in the second container for solid-phase sintering, so that chemicals such as acid or alkali and the like which cause serious pollution to the environment are not needed, and the preparation method has remarkable advantages of environmental protection;
(3) the preparation method of the magnetic refrigeration material provided by the invention is a solid-phase reaction method, has the advantages of simple preparation process, short reaction period and low energy consumption, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a comparison graph of an X-ray diffraction spectrum and a theoretical spectrum of a magnetic refrigeration material in examples 1 to 4 of the present invention.
FIG. 2 is a comparison graph of an X-ray diffraction spectrum and a theoretical spectrum of the magnetic refrigeration material in examples 5 to 8 of the present invention.
FIG. 3 is a comparison graph of an X-ray diffraction pattern and a theoretical pattern of the magnetic refrigeration material in comparative examples 1 to 2 of the present invention.
Fig. 4 is a thermomagnetic curve of Zero Field Cooling (ZFC) and band Field Cooling (FC) of the magnetic refrigeration material in embodiment 2 of the present invention under a 0.01T magnetic field.
Fig. 5 is the first derivative of the Zero Field Cooling (ZFC) thermomagnetic curve.
FIG. 6 is an isothermal magnetization curve of the magnetic refrigeration material of embodiment 2 of the present invention at 2-20K under a 0-5T magnetic field variation.
FIG. 7 is a graph showing the relationship between the magnetic entropy change and the temperature of the magnetic refrigeration material under the magnetic field change of 0.2-5T in embodiment 2 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
First, an embodiment
Example 1
The embodiment provides a preparation method of a magnetic refrigeration material, which comprises the following steps:
(1) LiF and GdF are weighed in a mass ratio of 1:13Grinding to obtain a mixture with the average particle size of 100 mu m;
(2) putting the mixture obtained in the step (1) into a first crucible made of corundum, and covering a cover of the first crucible;
(3) putting the first crucible into a second crucible made of graphite, spreading the graphite with the average grain diameter of 100 mu m outside the first crucible, and covering a cover of the second crucible;
(4) and (3) placing the second crucible into a tube furnace, and sintering for 10min at 1200 ℃ under the argon atmosphere to obtain the magnetic refrigeration material.
Example 2
The embodiment provides a preparation method of a magnetic refrigeration material, which comprises the following steps:
(1) LiF and GdF are weighed in a ratio of the amounts of the substances of 1.8:13Ball milling to obtain mixture with average grain size of 50 micron;
(2) putting the mixture obtained in the step (1) into a first crucible made of boron nitride, and covering a cover of the first crucible;
(3) putting the first crucible into a second crucible made of corundum, spreading carbon black with the average particle size of 500 mu m outside the first crucible, and covering a cover of the second crucible;
(4) and (3) placing the second crucible in a muffle furnace, and sintering for 40min at 1000 ℃ in an air atmosphere to obtain the magnetic refrigeration material.
Example 3
The embodiment provides a preparation method of a magnetic refrigeration material, which comprises the following steps:
(1) LiF and GdF are weighed in a ratio of the amounts of the substances of 1.4:13Mixing the powder to obtain a mixture with the average grain diameter of 100 mu m;
(2) putting the mixture obtained in the step (1) into a first crucible made of graphite, and covering a cover of the first crucible;
(3) putting the first crucible into a second crucible made of zirconia, spreading activated carbon with the average grain diameter of 200 mu m outside the first crucible, and covering a cover of the second crucible;
(4) and (3) placing the second crucible into a vacuum furnace, and sintering for 60min at 800 ℃ in a nitrogen atmosphere to obtain the magnetic refrigeration material.
Example 4
The embodiment provides a preparation method of a magnetic refrigeration material, which comprises the following steps:
(1) LiF and GdF are weighed in a mass ratio of 2:13Ball milling to obtain mixture with average grain size of 50 micron;
(2) putting the mixture obtained in the step (1) into a first crucible made of zirconia, and covering a cover of the first crucible;
(3) putting the first crucible into a second crucible made of silicon nitride, spreading coke with the average grain diameter of 200 mu m outside the first crucible, and covering a cover of the second crucible;
(4) and (3) placing the second crucible in a muffle furnace, and sintering for 30min at 1100 ℃ in an air atmosphere to obtain the magnetic refrigeration material.
Example 5
This example provides a method for preparing a magnetic refrigeration material, which is different from example 2 only in LiF and GdF3The ratio of the amounts of the substances (A) to (B) was 0.8:1, and the rest was the same as in example 2.
Example 6
This example provides a method for producing a magnetic refrigeration material, which is different from example 2 only in that the sintering temperature in step (4) is controlled to 700 ℃, and the rest is the same as example 2.
Example 7
This example provides a method for producing a magnetic refrigeration material, which is different from example 2 only in that the sintering temperature in step (4) is controlled to 1300 ℃, and the rest is the same as example 2.
Example 8
This example provides a method for producing a magnetic refrigeration material, which is different from example 2 only in that the sintering time in step (4) is controlled to 120min, and the rest is the same as example 2.
Example 9
This example provides a method for preparing a magnetic refrigeration material, which is different from example 2 only in LiF and GdF3The ratio of the amounts of the substances of (1) was 2.2:1, and the rest was the same as in example 2.
Too high a LiF content in this example results in a large LiF residue in the product and a desired phase composition is not obtained.
Example 10
This example provides a method for producing a magnetic refrigeration material, which is different from example 2 only in that the sintering time in step (4) is controlled to be 5min, and the rest is the same as example 2.
In this embodiment, too short sintering time may result in insufficient solid-phase reaction, and thus the desired magnetic refrigeration material may not be obtained.
Second, comparative example
Comparative example 1
This comparative example provides a production method of a magnetic refrigeration material, which is different from example 2 only in that the first container is not placed in the second container in step (3), and the rest is the same as example 2.
Specifically, the step (3) is as follows:
(3) and (3) spreading the carbon black with the average particle size of 500 mu m outside the first crucible in the step (2).
Comparative example 2
This comparative example provides a production method of a magnetic refrigeration material, which differs from example 2 only in that carbon black is not spread outside the first container in step (3), and the rest is the same as example 2.
Third, test and results
The magnetic refrigeration materials prepared in examples 1 to 8 and comparative examples 1 to 2 were subjected to phase analysis by X-ray powder diffraction using an X-ray diffractometer (XRD) model D8A a25 manufactured by Brucker. Wherein, fig. 1 is a comparison graph of an X-ray diffraction pattern and a theoretical pattern of a magnetic refrigeration material in examples 1 to 4 of the present invention, fig. 2 is a comparison graph of an X-ray diffraction pattern and a theoretical pattern of a magnetic refrigeration material in examples 5 to 8 of the present invention, and fig. 3 is a comparison graph of an X-ray diffraction pattern and a theoretical pattern of a magnetic refrigeration material in comparative examples 1 to 2 of the present invention.
FIG. 1 shows that the XRD patterns of the magnetic refrigeration materials in examples 1-4 are well matched with the theoretical patterns, which indicates that the magnetic refrigeration materials in examples 1-4 have high purity and are all single LiGdF4Phase composition belonging to tetragonal system and space group I41/a，α＝β＝γ＝90°。
FIG. 2 shows that the X-ray diffraction patterns of the magnetic refrigeration materials in examples 5-8 have obvious mixed peaks near 26 degrees, which indicates that impurity phases exist in the materials, and pure-phase LiGdF cannot be obtained4。
FIG. 3 shows that the X-ray diffraction patterns of the magnetic refrigeration materials in comparative examples 1-2 have obvious impurity peaks near 16 degrees and 28 degrees, which indicates that impurity phases obviously exist in the materials, and pure-phase LiGdF cannot be obtained4。
In conclusion, the selection of the technical parameters of the invention has very important significance, and the phase composition of the material can be influenced by insufficient or too much LiF dosage, too low or too high sintering temperature, too short or too long sintering time and the like, so that the pure-phase magnetic refrigeration material cannot be obtained.
Fig. 4 is a thermomagnetic curve of Zero Field Cooling (ZFC) and band Field Cooling (FC) in a 0.01T magnetic field of the magnetic refrigeration material in embodiment 2 of the present invention, and fig. 5 is a first derivative of the thermomagnetic curve of Zero Field Cooling (ZFC). As can be seen from fig. 4 and 5, the phase transition temperature of the magnetic refrigeration material in embodiment 2 is below 2K, and the material is a low-temperature magnetic refrigeration material, and the ZFC and FC thermal-magnetic curves of the material are completely overlapped, which indicates that the magnetic phase transition process is highly reversible, and has no thermal hysteresis, and is beneficial to the practical application of the magnetic refrigeration material.
FIG. 6 is an isothermal magnetization curve of the magnetic refrigeration material in example 2 of the present invention at 2-20K under a magnetic field change of 0-5T, where a solid curve of 2K is a magnetic field increasing process, and a hollow curve of 2K is a magnetic field decreasing process, and it can be seen from the graph that the magnetic refrigeration material in example 2 is paramagnetic at a higher temperature (>10K), and the magnetization intensity increases with a decrease in temperature; the magnetization intensity of the magnetic refrigeration material rapidly increases with the rise of an external magnetic field at the temperature of 2K, the magnetic refrigeration material tends to be saturated when the magnetic field is 5T, and the magnetization curves of the rising field and the falling field are almost overlapped, so that the magnetic refrigeration material is further explained to have no obvious thermal hysteresis and hysteresis loss.
And the magnetic entropy change under different magnetic field changes can be calculated according to isothermal magnetization curves under different temperatures by utilizing the Maxwell relation. FIG. 7 is a relationship between magnetic entropy change and temperature of a magnetic refrigeration material in embodiment 2 of the present invention under a magnetic field change of 0.2 to 5T, and it can be seen from the graph that the maximum magnetic entropy change of the magnetic refrigeration material in embodiment 2 monotonically increases with an increase in the external magnetic field, and the maximum magnetic entropy change of the magnetic refrigeration material gradually increases with a decrease in temperature under a certain external magnetic field; the maximum magnetic entropy change values of the magnetic field change of 1.5T, 2T and 5T are respectively 20 J.kg at the temperature of 2.5K-1·K-1、29J·kg-1·K-1And 58 J.kg-1·K-1。
TABLE 1
| Maximum magnetic entropy change (J.kg) under 2.5K, 5T magnetic field variation-1·K-1) | |
| Example 1 | 57 |
| Example 2 | 58 |
| Example 3 | 58 |
| Example 4 | 56 |
Table 1 shows the calculated magnetic entropy changes of the magnetic refrigeration materials in examples 1 to 4, and it can be seen from Table 1 that the maximum magnetic entropy change of the magnetic refrigeration materials in examples 1 to 4 is not less than 56 J.kg at a temperature of 2.5K under a magnetic field change of 0 to 5T-1·K-1The maximum reaches 58 J.kg-1·K-1All show strong magnetocaloric effect.
In summary, the present invention provides a magnetic refrigeration material and a method for preparing the same, which has a magnetocaloric property significantly better than that of the prior art materials and most of the reported magnetic refrigeration materials (e.g. ErMn) under the same conditions2Si2HoCuSi, TmCuAl, etc.), which are magnetic refrigeration materials having excellent performance.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A magnetic refrigeration material, characterized in that the magnetic refrigeration material comprises LiGdF4。
2. The magnetic refrigeration material as claimed in claim 1, wherein the maximum magnetic entropy change of the magnetic refrigeration material is less than or equal to 58J-kg under the condition of 0-5T magnetic field change at the temperature of 2.5K-1·K-1；
Preferably, the maximum magnetic entropy change of the magnetic refrigeration material is less than or equal to 29J-kg under the condition of 0-2T magnetic field change at the temperature of 2.5K-1·K-1；
Preferably, the magnetic refrigeration material changes in a magnetic field of 0-1.5T at a temperature of 2.5KThe maximum magnetic entropy change is less than or equal to 20 J.kg-1·K-1。
3. The magnetic refrigeration material according to claim 1 or 2, characterized in that the magnetic refrigeration material is a polycrystalline material;
preferably, the magnetic refrigeration material is tetragonal system;
preferably, the space group of the magnetic refrigeration material is I41/a。
4. A method for preparing a magnetic refrigeration material according to any one of claims 1 to 3, characterized by comprising the steps of:
(1) mixing LiF and GdF3Obtaining a mixture;
(2) placing the mixture of step (1) in a first container, and sealing the first container;
(3) putting the first container obtained in the step (2) into a second container, spreading carbon powder outside the first container, and sealing the second container;
(4) and (4) sintering the second container in the step (3) to obtain the magnetic refrigeration material.
5. The method of claim 4, wherein said LiF and GdF of step (1)3The ratio of the amount of the substance(s) is (1-2) to 1;
preferably, the LiF and GdF3The amount ratio of the substances (1.2-1.8) to (1);
preferably, the LiF and GdF3The amount ratio of the substances (1.6-1.8) to (1);
preferably, the mixing is done in a mortar, ball mill or blender;
preferably, the mixture has an average particle size of 100 μm or less.
6. The production method according to claim 4 or 5, wherein the first container of step (2) comprises a first crucible;
preferably, the material of the first crucible comprises corundum, quartz, graphite, zirconia, boron nitride, silicon carbide or silicon nitride.
7. The production method according to any one of claims 4 to 6, wherein the second container of step (3) comprises a second crucible;
preferably, the material of the second crucible comprises corundum, graphite, zirconia, silicon carbide or silicon nitride;
preferably, the carbon powder comprises any one or a combination of at least two of graphite, activated carbon, coke or carbon black;
preferably, the average particle size of the carbon powder is less than or equal to 500 mu m.
8. The production method according to any one of claims 4 to 7, wherein the sintering in the step (4) is performed in a sintering furnace;
preferably, the sintering furnace comprises a muffle furnace, a tube furnace or a vacuum furnace;
preferably, the sintering temperature is 800-1200 ℃;
preferably, the sintering time is 10-60 min;
preferably, the sintering is performed under an air atmosphere or an inert atmosphere;
preferably, the inert atmosphere comprises argon and/or nitrogen.
9. The method according to any one of claims 4 to 8, wherein the method comprises the steps of:
(1) mixing LiF and GdF according to the mass ratio of (1-2) to 13To obtain a mixture with the average grain diameter less than or equal to 100 mu m;
(2) placing the mixture of step (1) in a first container, and sealing the first container;
(3) putting the first container in the step (2) into a second container, fully spreading carbon powder with the average particle size of less than or equal to 500 mu m outside the first container, and sealing the second container;
(4) and (4) placing the second container in the step (3) into a sintering furnace, and sintering at the temperature of 800-1200 ℃ for 10-60 min to obtain the magnetic refrigeration material.
10. Use of a magnetic refrigeration material according to any one of claims 1 to 3 in the fields of low-temperature physics, space exploration and aerospace.
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