CN115557513B - Gadolinium-based borate compound, preparation and application thereof - Google Patents

Gadolinium-based borate compound, preparation and application thereof Download PDF

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CN115557513B
CN115557513B CN202211267139.3A CN202211267139A CN115557513B CN 115557513 B CN115557513 B CN 115557513B CN 202211267139 A CN202211267139 A CN 202211267139A CN 115557513 B CN115557513 B CN 115557513B
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涂衡
陈语葳
沈俊
戴巍
李振兴
张国春
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention provides a gadolinium-based borate compound, a preparation method and application thereof. The chemical formula of the gadolinium borate compound is Ba 2 Gd(BO 3 ) 2 F, belonging to orthorhombic system, the space group is Pnma, and the unit cell parameters are as follows: α=β=γ=90°, z=2. The gadolinium-based borate compound has magnetic cation Gd 3+ Has higher spin ground state and smaller magnetic anisotropy under the introduction of (A) and is magnetic cation Gd 3+ Providing ligands of smaller volume and relative molecular mass, beneficial for Gd 3+ And the filling space is provided as much as possible, the magnetic density of the crystal is improved, the crystal has a larger magnetic entropy change value and higher refrigeration efficiency, and the guidance significance is provided for practical application.

Description

Gadolinium-based borate compound, preparation and application thereof
Technical Field
The invention belongs to the technical field of magnetic refrigeration materials, and particularly relates to a gadolinium-based borate compound, a preparation method and an application thereof.
Background
The low-temperature refrigeration technology plays a very important role in the fields of gas liquefaction, high-energy physics, superconducting technology, aerospace and the like. At present, the low temperature is mainly obtained and maintained by utilizing the compression-expansion cycle of liquid helium, but the efficiency is lower, the reliability is not high, rare and expensive helium-3 is generally required to be used in a temperature range below 2K, and the research and application of the low temperature range are limited.
The magnetic refrigeration technology has the advantages of high efficiency, low energy consumption and green environmental protection, is known as the green refrigeration technology, is valued by various countries in the world, utilizes the magneto-caloric effect, mainly relies on isothermal magnetization and adiabatic demagnetization to realize the cooling of the surrounding environment, and particularly measures the magnetic entropy change of magnetic substances along with the change of an external magnetic field in an isothermal state. When the externally applied magnetic field is zero, the magnetic moment direction in the material is disordered, and the magnetic entropy is larger; applying a magnetic field under isothermal conditions, enabling the magnetic moment orientation to be consistent, reducing magnetic entropy, enabling the adiabatic temperature of a system to rise by applying work to materials by the magnetic field, and releasing heat to the environment; and then the external magnetic field is removed under the adiabatic condition, the magnetic moment is restored to a disordered state, the magnetic entropy is increased, the adiabatic temperature of the system is reduced, and the heat is absorbed into the external environment, so that the aim of refrigeration is fulfilled.
For a magnetic refrigeration material with excellent performance, a larger magnetic entropy change value is required, and the magnetic molecules are required to have a large spin ground state, small magnetic anisotropy, high magnetic density, proper magnetic exchange and low-energy excited spin state. Gd (Gd) 3+ Ions have half-full 4f electron shells, the ground state is spin-big, the magnetic anisotropy is negligible, gadolinium-based compounds can be used as good low-temperature magnetic refrigeration materials, borates have high thermal stability and high thermal conductivity, and paramagnetic salts have low hysteresis effects and can be used as good magnetic refrigeration materials.
Therefore, research on a new gadolinium-based borate compound is of great significance in the field of magnetic refrigeration.
Disclosure of Invention
A first object of the present invention is to provide a gadolinium based borate compound. The gadolinium-based borate compound has magnetic cation Gd 3+ Has higher introduction ratio ofAnd smaller magnetic anisotropy, while being magnetic cationic Gd 3+ Providing ligands of smaller volume and relative molecular mass, beneficial for Gd 3+ And the filling space is provided as much as possible, the magnetic density of the crystal is improved, the crystal has a larger magnetic entropy change value and higher refrigeration efficiency, and the guidance significance is provided for practical application.
A second object of the present invention is to provide a process for preparing gadolinium based borate compounds as described above.
A third object of the present invention is to provide the use of gadolinium based borate compounds as described above in the field of magnetic refrigeration.
In order to achieve the first object, the present invention adopts the technical scheme that:
the invention discloses a gadolinium-based borate compound, the chemical formula of which is Ba 2 Gd(BO 3 ) 2 F, belonging to orthorhombic system, the space group is Pnma, and the unit cell parameters are as follows:α＝β＝γ＝90°，Z＝2。
in order to further expand the variety selection of magnetic refrigeration materials such as gadolinium-based borate compounds, the invention uses Gd 3+ Is a magnetic cation, BO with small molecular weight 3 3- A novel gadolinium borate compound is successfully synthesized as a ligand. Ligand BO of smaller volume and relative molecular mass when constructing the basic framework of a compound 3 3- Is a magnetic cation Gd with larger volume 3+ Providing as much filling space as possible, ensuring that certain spacing exists between magnetic cations to have less magnetic interaction, increasing the mass ratio of rare earth to ligand as much as possible to increase the magnetic density of the crystal, and simultaneously, BO with small molecular weight 3 3- As a ligand, the processing difficulty of the crystal in the practical application process can be reduced, and the refrigeration stability of the crystal can be improved. Through reasonable element collocation, the magnetic refrigeration material is more suitable for a 2K magnetic field system with lower temperature, and has higher magnetic entropy change value and preparation compared with the magnetic refrigeration material in the prior artThe cold efficiency is a magnetic refrigeration material with excellent performance.
In order to achieve the second object, the present invention adopts the technical scheme that:
the invention discloses a method for preparing gadolinium-based borate compound, which comprises the following steps:
uniformly mixing a Ba-containing compound, a Gd-containing compound, a B-containing compound and an F-containing compound, uniformly heating to 650-700 ℃ in an aerobic environment, presintering at a constant temperature, cooling for one time, and grinding; and in a vacuum environment, heating to 770-780 ℃ again at a constant speed, reacting at a constant temperature, cooling again, and grinding to obtain gadolinium-based borate crystals.
Further, in the Ba-containing compound, the Gd-containing compound, the B-containing compound and the F-containing compound, the mol ratio of the elements Ba, gd, B and F is 1-3:1:1-3:1-2; preferably, when the molar ratio of the elements Ba, gd, B and F in the Ba-containing compound, gd-containing compound, B-containing compound and F-containing compound is 2:1:2:1, the hetero-phase ratio of the target product may be further reduced to obtain single crystal Ba 2 Gd(BO 3 ) 2 And F compound.
Further, the Ba-containing compound is selected from a Ba-containing carbonate or a Ba-containing fluoride; preferably, the Gd-containing compound is selected from Gd-containing oxides; preferably, the B-containing compound is selected from H 3 BO 3 Or B is a 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the F-containing compound is BaF 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the O source is selected from BaCO 3 、Gd 2 O 3 、H 3 BO 3 、B 2 O 3 One or more of them.
Further, the temperature rising speed of the uniform temperature rising or the uniform temperature rising again is 30-40 ℃/h.
Further, the constant-temperature presintering time is 2-3d. Wherein the constant temperature calcination aims at removing H in the reactant 2 O and CO 2 And a preliminary solid phase reaction is carried out, the aerobic environment being preferably an air atmosphere.
Further, the primary cooling is performed at a cooling rate of 40-50 ℃/h.
Further, the secondary cooling is performed at a cooling rate of 30-40 ℃/h.
In order to achieve the third object, the present invention adopts the technical scheme that:
the invention discloses application of the gadolinium-based borate compound or the gadolinium-based borate compound obtained by the preparation method in the field of magnetic refrigeration.
Further, the refrigeration effect achieved when the gadolinium-based borate compound is applied to a magnetic field system under the condition of 2K is optimal.
The invention has the beneficial effects that:
the invention provides a gadolinium-based borate compound, a preparation method and application thereof. In order to further expand the variety selection of magnetic refrigeration materials such as gadolinium-based borate compounds, the invention uses Gd 3+ Is a magnetic cation, BO with small molecular weight 3 3- A novel gadolinium borate compound is successfully synthesized as a ligand. Ligand BO of smaller volume and relative molecular mass when constructing the basic framework of a compound 3 3- Is a magnetic cation Gd with larger volume 3+ Providing as much filling space as possible, ensuring that certain spacing exists between magnetic cations to have less magnetic interaction, increasing the mass ratio of rare earth to ligand as much as possible to increase the magnetic density of the crystal, and simultaneously, BO with small molecular weight 3 3- As a ligand, the processing difficulty of the crystal in the practical application process can be reduced, and the refrigeration stability of the crystal can be improved. Through reasonable element collocation, the magnetic refrigeration material is more suitable for a 2k magnetic field system with lower temperature, has higher magnetic entropy change value and refrigeration efficiency compared with the magnetic refrigeration material in the prior art, and is a magnetic refrigeration material with excellent performance.
Drawings
FIG. 1 shows the crystal Ba prepared in example 1 2 Gd(BO 3 ) 2 XRD pattern of F.
FIG. 2 shows the crystal Ba prepared in example 1 2 Gd(BO 3 ) 2 F, structural schematic diagram.
FIG. 3 shows the crystal Ba prepared in example 1 2 Gd(BO 3 ) 2 F infrared spectrum.
FIG. 4 shows the crystal Ba prepared in example 1 2 Gd(BO 3 ) 2 F thermogram.
FIG. 5 shows the crystal Ba prepared in example 1 2 Gd(BO 3 ) 2 F temperature change susceptibility curve and curie-gaussian fitting curve.
FIG. 6 shows the crystal Ba prepared in example 1 2 Gd(BO 3 ) 2 F temperature and field magnetization diagram.
FIG. 7 shows the crystal Ba prepared in example 1 2 Gd(BO 3 ) 2 Arrott plot of F.
FIG. 8 shows the crystal Ba prepared in example 1 2 Gd(BO 3 ) 2 F magnetic entropy change diagram.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It should be understood that the described embodiments are merely some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing powdered Ba by high-temperature solid phase method 2 Gd(BO 3 ) 2 F crystal comprising the steps of:
BaCO is weighed 3 ：2.36g(12mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，B 2 O 3 : mixing 0.56g (8 mmol), loading into an open platinum crucible with phi 20mm multiplied by 20mm, compacting, placing into a muffle furnace, heating to 700 ℃ at a heating rate of 30 ℃/h in an air environment, presintering at a constant temperature for 2d, cooling to room temperature at a rate of 50 ℃/h, and grinding to obtain a preliminary presintering product. Pouring the presintered product into a quartz glass tube, vacuumizing and sealing, placing into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grindingGrinding to obtain Ba 2 Gd(BO 3 ) 2 Powder sample of F crystals.
Ba prepared in this example 2 Gd(BO 3 ) 2 The F crystal samples were tested as follows:
structural characterization:
XRD was used for the Ba obtained in this example 2 Gd(BO 3 ) 2 F crystal is characterized, and the result is shown in FIG. 1, in which Ba 2 Gd(BO 3 ) 2 F is an orthorhombic system, the space group is Pnma, and the unit cell parameters are as follows: α＝β＝γ＝90°，Z＝2。
ba prepared in this example 2 Gd(BO 3 ) 2 The F structure is schematically shown in FIG. 2.
FIG. 3 shows the Ba obtained in this example 2 Gd(BO 3 ) 2 F crystal infrared spectrum characterization result, BO is shown in the figure 3 3- The asymmetric stretching vibration peaks of (C) are 1262 cm and 1199cm -1 ，BO 3 3- The symmetrical stretching vibration peak of (C) is 935cm -1 ，BO 3 3- Bending vibration peaks at 739 and 594cm -1 . The infrared spectrum shows Ba 2 Gd(BO 3 ) 2 The coordination mode of B in the F crystal is BO 3 Is matched with the actual structure.
Thermal stability test:
the Ba is 2 Gd(BO 3 ) 2 The thermogravimetric analysis result of the F crystal is shown in fig. 4, which shows that the crystal material has good stability in the temperature range from room temperature to 1150 ℃ and no phase change and quality loss.
Magnetic testing:
the following magnetocaloric effect study was performed with a Quantum Design PPMS-9 complex system in the range of 2K-300K under a magnetic field of 0T-9T:
at a temperature ranging from 2K to 300K, magneticBa was measured in the field range of 0-9T 2 Gd(BO 3 ) 2 The temperature change magnetic susceptibility and the temperature change magnetic susceptibility reciprocal curve of the F crystal are shown in figure 5. The reciprocal curve of the variable-temperature magnetic susceptibility is linearly fitted according to the Curie-Curie theorem, so that the compound is a paramagnetic salt material, and the Curie constant C=7.47 emu K mol -1 The gaussian constant θ=2.13K, and positive gaussian constant accounts for Ba 2 Gd(BO 3 ) 2 The extremely weak ferromagnetic coupling effect of the F crystal is suitable for being used as a magnetic refrigeration material.
Ba measured at a temperature ranging from 2K to 10K and a magnetic field ranging from 0 to 9T 2 Gd(BO 3 ) 2 The temperature and field magnetization diagram of the F crystal is shown in fig. 6. The curve shows that Ba as the strength of the magnetic field increases 2 Gd(BO 3 ) 2 The magnetization of the F crystal gradually increases and reaches a saturation value of 6.77N mu at a temperature of 2K and a magnetic field of 9T Β And theoretical value 7N mu Β Is very close.
Ba 2 Gd(BO 3 ) 2 The phase change type of the F crystal can be according to Banerjee criterion: the magnetization data of the variable temperature and variable field are used for estimation, the obtained result is shown as an Arrott curve in FIG. 7, the slope of each point on the curve is positive, and the magnetic phase transition of the crystal material is indicated to belong to the second-level magnetic phase transition.
Ba 2 Gd(BO 3 ) 2 The change in magnetic entropy of the F crystal can be according to the Maxwell formula: the magnetization data of the temperature and field change are used for estimation, the obtained result is shown as a magnetic entropy curve in fig. 8, and the crystal material in the test range is known to be 2K, delta mu 0 The maximum magnetic entropy change value of 27.82J kg is shown when H=9T -1 K -1 。
Example 2
Preparing powdered Ba by high-temperature solid phase method 2 Gd(BO 3 ) 2 F crystal comprising the steps of:
BaCO is weighed 3 ：2.36g(12mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，H 3 BO 3 :0.99g (16 mmol) of the mixture is evenly mixed and put into an open platinum crucible with phi of 20mm multiplied by 20mm, compacted and put into a muffle furnaceHeating to 700 ℃ at a heating rate of 30 ℃/h in an air environment, presintering for 2 days at a constant temperature, cooling to room temperature at a rate of 50 ℃/h, and grinding to obtain a preliminary presintering product. Pouring the presintered product into a quartz glass tube, vacuumizing and sealing, placing into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain Ba 2 Gd(BO 3 ) 2 Powder sample of F crystals.
XRD was used for the Ba obtained in this example 2 Gd(BO 3 ) 2 The F crystal was characterized and the results were substantially identical to example 1.
Example 3
Preparing powdered Ba by high-temperature solid phase method 2 Gd(BO 3 ) 2 F crystal comprising the steps of:
BaCO is weighed 3 ：2.36g(12mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，H 3 BO 3 :0.49g (8 mmol) and B 2 O 3 :0.28g (4 mmol) of the mixture is uniformly mixed, the mixture is filled into an open platinum crucible with phi of 20mm multiplied by 20mm, the mixture is compacted and put into a muffle furnace, the temperature is increased to 700 ℃ at a heating rate of 30 ℃/h in an air environment, the mixture is presintered for 2d at a constant temperature, then the mixture is cooled to room temperature at a rate of 50 ℃/h, and a preliminary presintered product is obtained after grinding. Pouring the presintered product into a quartz glass tube, vacuumizing and sealing, placing into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain Ba 2 Gd(BO 3 ) 2 Powder sample of F crystals.
XRD was used for the Ba obtained in this example 2 Gd(BO 3 ) 2 The F crystal was characterized and the results were substantially identical to example 1.
Example 4
Preparing powdered Ba by high-temperature solid phase method 2 Gd(BO 3 ) 2 F crystal comprising the steps of:
BaCO is weighed 3 ：2.36g(12mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，H 3 BO 3 :0.49g (8 mmol) and B 2 O 3 :0.28g (4 mmol) of the mixture is uniformly mixed, the mixture is filled into an open platinum crucible with phi of 20mm multiplied by 20mm, the mixture is compacted and put into a muffle furnace, the temperature is increased to 700 ℃ at a heating rate of 30 ℃/h in an air environment, the mixture is presintered for 1d at a constant temperature, then the mixture is cooled to room temperature at a rate of 50 ℃/h, and a preliminary presintered product is obtained after grinding. Pouring the presintered product into a quartz glass tube, vacuumizing and sealing, placing into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain Ba 2 Gd(BO 3 ) 2 Powder sample of F crystals.
XRD was used for the Ba obtained in this example 5 Gd 3 (BO 3 ) 6 Characterization was performed with F, and the results were substantially identical to example 1.
Comparative example 1
The method for preparing the crystal by adopting the high-temperature solid phase method comprises the following steps:
BaCO is weighed 3 ：2.37g(12mmol)，Gd 2 O 3 ：0.72g(2mmol)，GdF 3 :0.43g (2 mmol) and B 2 O 3 :0.42g (6 mmol) of the mixture is uniformly mixed, the mixture is filled into an open platinum crucible with phi of 20mm multiplied by 20mm, the mixture is compacted and put into a muffle furnace, the temperature is increased to 700 ℃ at a heating rate of 30 ℃/h in an air environment, the mixture is presintered for 1d at a constant temperature, then the mixture is cooled to room temperature at a rate of 50 ℃/h, and a preliminary presintered product is obtained after grinding. And pouring the presintered product into a quartz glass tube, vacuumizing and sealing, putting into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain a powder sample.
Characterization of the powder sample obtained in this example by XRD revealed that XRD of the powder sample in this example was not consistent with that in example 1, i.e., the target product Ba could not be synthesized 2 Gd(BO 3 ) 2 And F, crystal.
Comparative example 2
The method for preparing the crystal by adopting the high-temperature solid phase method comprises the following steps:
BaCO is weighed 3 ：2.36g(12mmol)，BaCl 2 ：0.83g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，B 2 O 3 : mixing 0.56g (8 mmol), loading into an open platinum crucible with phi 20mm multiplied by 20mm, compacting, placing into a muffle furnace, heating to 700 ℃ at a heating rate of 30 ℃/h in an air environment, presintering at a constant temperature for 2d, cooling to room temperature at a rate of 50 ℃/h, and grinding to obtain a preliminary presintering product. And pouring the presintered product into a quartz glass tube, vacuumizing and sealing, putting into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain a powder sample.
Characterization of the powder sample obtained in this example by XRD revealed that the XRD spectrum of the powder sample in this example is not identical to that of example 1, i.e., the target product Ba could not be synthesized 2 Gd(BO 3 ) 2 And F, crystal.
Comparative example 3
Preparing powdered Ba by high-temperature solid phase method 2 Gd(BO 3 ) 2 F crystal comprising the steps of:
BaCO is weighed 3 ：2.75g(14mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，B 2 O 3 : mixing 0.56g (8 mmol), loading into an open platinum crucible with phi 20mm multiplied by 20mm, compacting, placing into a muffle furnace, heating to 700 ℃ at a heating rate of 30 ℃/h in an air environment, presintering at a constant temperature for 1d, cooling to room temperature at a rate of 50 ℃/h, and grinding to obtain a preliminary presintering product. Pouring the presintered product into a quartz glass tube, vacuumizing and sealing, placing into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain Ba 2 Gd(BO 3 ) 2 Powder sample of F crystals.
Characterization of the powder sample obtained in this example by XRD revealed that the XRD spectrum of the powder sample in this example is not identical to that of example 1, i.e., the target product Ba could not be synthesized 2 Gd(BO 3 ) 2 And F, crystal.
Comparative example 4
The method for preparing the crystal by adopting the high-temperature solid phase method comprises the following steps:
BaCO is weighed 3 ：2.36g(12mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，B 2 O 3 : mixing 0.56g (8 mmol), loading into an open platinum crucible with phi 20mm multiplied by 20mm, compacting, placing into a muffle furnace, heating to 700 ℃ at a heating rate of 30 ℃/h in an air environment, presintering at a constant temperature for 2d, cooling to room temperature at a rate of 50 ℃/h, and grinding to obtain a preliminary presintering product. Pouring the presintered product into a quartz glass tube in air, putting into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain a powder sample.
Characterization of the powder sample obtained in this example by XRD revealed that the XRD spectrum of the powder sample in this example is not identical to that of example 1, i.e., the target product Ba could not be synthesized 2 Gd(BO 3 ) 2 And F, crystal.
Comparative example 5
The preparation method of the crystal by adopting the aqueous solution method comprises the following steps:
BaCO is weighed 3 ：2.36g(12mmol)，BaF 2 ：0.70g(4mmol)，Gd 2 O 3 ：1.44g(4mmol)，B 2 O 3 :0.56g (8 mmol) was placed in a 100mL glass beaker, dissolved in 40% strength by volume concentrated nitric acid, and placed in an oven at 200℃until oven dried. Placing the obtained white powder into an open platinum crucible with the diameter of 20mm multiplied by 20mm, compacting the white powder, placing the compact powder into a muffle furnace, heating the compact powder to 700 ℃ at a heating rate of 30 ℃/h in an air environment, presintering the compact powder at a constant temperature for 2d, cooling the compact powder to room temperature at a rate of 50 ℃/h, and grinding the compact powder to obtain a preliminary presintering product. And pouring the presintered product into a quartz glass tube, vacuumizing and sealing, putting into a muffle furnace, heating to 770 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain a powder sample.
Characterization of the powder sample obtained in this example by XRD revealed that the XRD spectrum of the powder sample in this example is not identical to that of example 1, i.e., the target product Ba could not be synthesized 2 Gd(BO 3 ) 2 And F, crystal.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (12)

1. The application of gadolinium-based borate compound in the field of magnetic refrigeration is characterized in that the chemical formula of the gadolinium-based borate compound is Ba 2 Gd(BO 3 ) 2 F, belonging to orthorhombic system, the space group is Pnma, and the unit cell parameters are as follows: α＝β＝γ＝90°，Z＝2。
2. the use according to claim 1, wherein the gadolinium borate compound is prepared according to the following steps:
uniformly mixing a Ba-containing compound, a Gd-containing compound, a B-containing compound and an F-containing compound, uniformly heating to 650-700 ℃ in an aerobic environment, presintering at a constant temperature, cooling for one time, and grinding; and in a vacuum environment, heating to 770-780 ℃ again at a constant speed, reacting at a constant temperature, cooling again, and grinding to obtain gadolinium-based borate crystals.
3. The use according to claim 2, wherein the molar ratio of the elements Ba, gd, B and F in the Ba-, gd-, B-and F-containing compounds is 1-3:1-2.
4. Use according to claim 2, characterized in that the molar ratio of the elements Ba, gd, B and F is 2:1:2:1.
5. Use according to claim 2, wherein the Ba-containing compound is selected from Ba-containing carbonates or Ba-containing fluorides.
6. The use according to claim 2, wherein the Gd-containing compound is selected from Gd-containing oxides.
7. The use according to claim 2, wherein the B-containing compound is selected from H 3 BO 3 Or B is a 2 O 3 。
8. The use according to claim 2, wherein the F-containing compound is BaF 2 。
9. Use according to claim 2, wherein the temperature increase rate of the constant temperature increase or the constant temperature increase again is 30-40 ℃/h.
10. The use according to claim 2, characterized in that the constant temperature burn-in time is 2-3d.
11. Use according to claim 2, wherein the primary cooling is performed at a cooling rate of 40-50 ℃/h.
12. Use according to claim 2, wherein the secondary cooling is carried out at a cooling rate of 30-40 ℃/h.
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