CN115020053B - R applied to magnetic refrigeration 2 TiNiO 6 Rare earth oxide and preparation method thereof - Google Patents
R applied to magnetic refrigeration 2 TiNiO 6 Rare earth oxide and preparation method thereof Download PDFInfo
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- CN115020053B CN115020053B CN202210619526.2A CN202210619526A CN115020053B CN 115020053 B CN115020053 B CN 115020053B CN 202210619526 A CN202210619526 A CN 202210619526A CN 115020053 B CN115020053 B CN 115020053B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
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Abstract
The invention belongs to the technical field of rare earth magnetic functional materials, and provides an R applied to magnetic refrigeration 2 TiNiO 6 Rare earth oxide, wherein R is one or two of Gd, tb and Dy 2 TiNiO 6 The oxide has a monoclinic crystal structure and belongs to a P21c space group; the R is 2 TiNiO 6 The maximum isothermal magnetic entropy change value of the oxide is 11.8J/kgK to 32.5J/kgK under the magnetic field change of 0T to 5T, and the maximum isothermal magnetic entropy change value is 15.9J/kgK to 43.8J/kgK under the magnetic field change of 0T to 7T. The invention has the advantages of low cost of raw materials, simple preparation method and good magnetic and thermal reversible properties. The method has simple process and is suitable for industrialization.
Description
Technical Field
The invention belongs to the technical field of rare earth magnetic functional materials, and particularly relates to an R applied to magnetic refrigeration 2 TiNiO 6 Rare earth oxide and a preparation method thereof.
Background
The magnetic refrigeration material is a novel magnetic functional material, and is a pollution-free refrigeration working medium material for realizing refrigeration by utilizing the magnetocaloric effect (also called magnetic card effect or magnetic entropy effect) of the magnetic material. The principle of magnetic refrigeration is that the magnetic moment of magnetic working medium is changed orderly and disorderly (phase change) by using external magnetic field to cause the heat absorption and release of magnet to perform refrigeration cycle. Magnetic refrigeration is a brand new refrigeration technology, and because the magnetic solid working medium has higher density, compared with the common compressed gas refrigeration mode, the volume of the magnetic refrigerator is smaller. In addition, the air conditioner does not discharge any harmful gas such as Freon and the like, and can consume 20-30% less energy compared with the best existing refrigeration system, so that the air conditioner is called as a 'green' refrigeration technology.
At present, the magnetic refrigeration technology is not widely applied, but the magnetic refrigeration has the advantages of simple structure, no pollution, high entropy density, small volume, high efficiency, low noise and the like compared with the traditional gas compression refrigeration, and is a new refrigeration mode with potential in the future. One of the key factors that depends on whether this technology can be taken out of the laboratory is the search for high performance magnetic refrigeration materials. At present, magnetic refrigeration materials are mainly high-purity rare earth or rare earth intermetallic compound materials, and the materials have the defects of high raw material price, complex preparation process and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an R applied to magnetic refrigeration 2 TiNiO 6 Rare earth oxide, wherein R is Gd, tb or DyOne or two of (a) and (b), the R is 2 TiNiO 6 The oxide has a monoclinic crystal structure and belongs to a P21c space group; the R is 2 TiNiO 6 The maximum isothermal magnetic entropy change value of the oxide is 11.8J/kgK to 32.5J/kgK under the magnetic field change of 0T to 5T, and the maximum isothermal magnetic entropy change value is 15.9J/kgK to 43.8J/kgK under the magnetic field change of 0T to 7T.
Also provides a magnetic refrigeration R 2 TiNiO 6 The preparation method of the rare earth oxide, wherein R is one or two of Gd, tb and Dy, comprises the following steps:
step 1: weighing rare earth nitrate, titanium nitrate and nickel nitrate according to a molar ratio of 2;
step 2: adding citric acid dissolved in ethanol into the mixture weighed in the step 1, wherein the mass ratio of the mixture weighed in the step 1 to the citric acid is 1.5-1;
and 3, step 3: after cooling, annealing the gel at 480-580 ℃ for 7-9 h to form a sinter;
and 4, step 4: grinding the sinter into powder, cold-pressing and molding by a tablet press, putting the powder into a corundum crucible, sintering the powder for 36 to 72 hours at 950 to 1050 ℃, and cooling the powder to room temperature along with the furnace to obtain the R 2 TiNiO 6 And (5) finishing.
Rare earth of the invention R 2 TiNiO 6 The maximum isothermal magnetic entropy change value of the oxide material can reach 11.8J/kgK to 32.5J/kgK under the magnetic field change of 0T to 5T, and can reach 15.9J/kgK to 43.8J/kgK under the magnetic field change of 0T to 7T. And has the advantages of low cost of raw materials, simple preparation method and good magnetic and thermal reversible properties. The method has simple process and is suitable for industrialization.
Detailed description of the preferred embodiments
The present invention is further analyzed by the following specific examples, which are not intended to limit the present invention in any way.
Example 1
Gd applied to magnetic refrigeration 2 TiNiO 6 Oxide materialThe preparation method comprises the following steps:
step 1: weighing 0.2mol of gadolinium nitrate, 0.1mol of titanium nitrate and 0.1mol of nickel nitrate;
and 2, step: adding citric acid dissolved in ethanol, wherein the mass of gadolinium nitrate is as follows: citric acid mass =1:1.8, quickly and fully stirring, heating to 75 ℃ to evaporate ethanol to dryness to form gel;
and step 3: after cooling, annealing the gel at 480 ℃ for 8h to form a sinter;
and 4, step 4: grinding the sinter into powder, tabletting and forming by a tablet press, placing into a corundum crucible, sintering for 48 hours at 1000 ℃ by a muffle furnace, and cooling to room temperature along with the furnace to obtain Gd 2 TiNiO 6 An oxide material.
Gd obtained in example 2 TiNiO 6 The oxide material was confirmed to have a monoclinic crystal structure by X-ray diffraction from Japan science, and belongs to the P21c space group.
Gd prepared in this example was measured on a Vibrating Sample Magnetometer (VSM) measuring accessory manufactured by Quantum design, USA 2 TiNiO 6 Under the magnetic field change of 0-5T and 0-7T, the isothermal magnetic entropy change maximum value of the oxide material reaches 32.5J/kgK and 43.8J/kgK respectively.
Example 2
Tb applied to magnetic refrigeration 2 TiNiO 6 The oxide material and the preparation method thereof comprise the following steps:
step 1: weighing 0.16mol of terbium nitrate, 0.08mol of titanium nitrate and 0.08mol of nickel nitrate;
step 2: adding citric acid dissolved in ethanol, wherein the mass of terbium nitrate is as follows: citric acid mass =1:2, quickly and fully stirring, heating to 85 ℃, and evaporating ethanol to dryness to form gel;
and step 3: after cooling, the gel was annealed at 520 ℃ for 8.5h to form a sinter;
and 4, step 4: grinding the sinter into powder, tabletting by a tabletting machine, placing into a corundum crucible, sintering at 1020 ℃ for 36h by a muffle furnace, and cooling to room temperature along with the furnace to obtain Tb 2 TiNiO 6 An oxide material.
Tb prepared in this example 2 TiNiO 6 The oxide material was confirmed to have a monoclinic crystal structure by X-ray diffraction from Japan science, and belongs to the P21c space group.
Tb prepared in this example and measured in a measuring part of a Vibration Sample Magnetometer (VSM) of a physical Property measuring System (PPMS-9) manufactured by Quantum design, USA 2 TiNiO 6 Under the magnetic field change of 0-5T and 0-7T, the isothermal magnetic entropy change maximum value of the oxide material respectively reaches 11.8J/kgK and 15.9J/kgK.
Example 3
GdDyTiNiO applied to magnetic refrigeration 6 The oxide material and the preparation method thereof comprise the following steps:
step 1: weighing 0.06mol of gadolinium nitrate, 0.06mol of dysprosium nitrate, 0.06mol of titanium nitrate and 0.06mol of nickel nitrate;
step 2: adding ethanol to dissolve citric acid, wherein the mass of (gadolinium nitrate + dysprosium nitrate) is as follows: citric acid mass =1:1.5, quickly and fully stirring, heating to 95 ℃ to evaporate ethanol to dryness to form gel;
and step 3: after cooling, the gel is annealed for 9h at 580 ℃ to form a sinter;
and 4, step 4: grinding the sinter into powder, tabletting and forming by a tabletting machine, placing the powder into a corundum crucible, sintering the powder for 70 hours at 1050 ℃ by using a muffle furnace, and cooling the powder to room temperature along with the furnace to obtain GdDyTiNiO 6 An oxide material.
GdDyTiNiO prepared in the example 6 The oxide material was confirmed to have a monoclinic crystal structure by X-ray diffraction from Japan science, and belongs to the P21c space group.
GdDyTiNiO made in this example, measured on a Vibrating Sample Magnetometer (VSM) measurement accessory manufactured by Quantum design, USA 6 Under the magnetic field change of 0-5T and 0-7T, the isothermal magnetic entropy change maximum value of the oxide material reaches 22.8J/kgK and 35.9J/kgK respectively.
Example 4
Gd applied to magnetic refrigeration 1.3 Tb 0.7 TiNiO 6 Oxide material and method for producing the sameThe method comprises the following steps:
step 1: weighing 0.13mol of gadolinium nitrate, 0.07mol of terbium nitrate, 0.1mol of titanium nitrate and 0.1mol of nickel nitrate;
and 2, step: adding citric acid dissolved in ethanol, wherein the mass of (gadolinium nitrate + terbium nitrate): citric acid mass =1:2.5, quickly and fully stirring, heating to 90 ℃, and evaporating ethanol to dryness to form gel;
and step 3: after cooling, the gel was annealed at 520 ℃ for 7h to form a sinter;
and 4, step 4: grinding the sinter into powder, tabletting by a tabletting machine, placing into a corundum crucible, sintering at 950 ℃ for 72 hours by a muffle furnace, and cooling to room temperature along with the furnace to obtain Gd 1.3 Tb 0.7 TiNiO 6 Oxide of silicon a material.
Gd obtained in example 1.3 Tb 0.7 TiNiO 6 The oxide material was confirmed to have a monoclinic crystal structure by X-ray diffraction from Japan science, and belongs to the P21c space group.
Gd prepared in this example was measured on a Vibrating Sample Magnetometer (VSM) measuring accessory manufactured by Quantum design, USA 1.3 Tb 0.7 TiNiO 6 Under the magnetic field change of 0-5T and 0-7T, the isothermal magnetic entropy change maximum value of the oxide material reaches 25.9J/kgK and 38.2J/kgK respectively.
Claims (2)
1.R 2 TiNiO 6 The magnetic refrigeration application of the rare earth oxide, wherein R is one or two of Gd, tb and Dy, is characterized in that,
said R is 2 TiNiO 6 The oxide has a monoclinic crystal structure and belongs to a P21c space group;
said R is 2 TiNiO 6 The maximum isothermal magnetic entropy change value of the oxide is 11.8J/kgK to 32.5J/kgK under the magnetic field change of 0T to 5T, and is 15.9J/kgK to 43.8J/kgK under the magnetic field change of 0T to 7T.
2. R according to claim 1 2 TiNiO 6 Use of rare earth oxides for magnetic refrigeration, characterized in thatR is 2 TiNiO 6 The preparation method of the rare earth oxide comprises the following steps:
step 1: weighing rare earth nitrate, titanium nitrate and nickel nitrate according to a molar ratio of 2;
step 2: adding citric acid dissolved in ethanol into the mixture weighed in the step 1, wherein the mass ratio of the mixture weighed in the step 1 to the citric acid is 1.5-1.5, quickly and fully stirring, heating to 75-95 ℃, and evaporating the ethanol to dryness to form gel;
and step 3: after cooling, annealing the gel at 480-580 ℃ for 7-9 h to form a sinter;
and 4, step 4: grinding the sinter into powder, cold-pressing and molding by a tablet press, putting the powder into a corundum crucible, sintering the powder for 36h to 72h at 950-1050 ℃, and furnace-cooling the powder to room temperature to obtain R 2 TiNiO 6 And (5) finishing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3813746B2 (en) * | 1998-09-25 | 2006-08-23 | 三洋電機株式会社 | Refrigeration system using hydrogen storage alloy |
| CN105347797B (en) * | 2015-10-10 | 2017-10-24 | 东北大学 | R in freezing applied to low temperature magnetic2Cu2O5Oxide material and preparation method thereof |
| CN110993230A (en) * | 2019-11-05 | 2020-04-10 | 杭州电子科技大学 | Rare earth RE applied to low-temperature magnetic refrigeration2MnCuO6Material and preparation method |
| CN111403137B (en) * | 2019-12-18 | 2022-07-08 | 上海大学 | Rare earth RE2ZnMnO6Oxide magnetic refrigeration material and preparation method thereof |
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