CN116469632B - Magneto-caloric material and preparation method and application thereof - Google Patents
Magneto-caloric material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116469632B CN116469632B CN202310567109.2A CN202310567109A CN116469632B CN 116469632 B CN116469632 B CN 116469632B CN 202310567109 A CN202310567109 A CN 202310567109A CN 116469632 B CN116469632 B CN 116469632B
- Authority
- CN
- China
- Prior art keywords
- magnetocaloric material
- magnetic
- source
- magnetocaloric
- gadolinium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000005291 magnetic effect Effects 0.000 claims abstract description 123
- 238000005057 refrigeration Methods 0.000 claims abstract description 36
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 22
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000004907 flux Effects 0.000 claims description 3
- 230000008859 change Effects 0.000 abstract description 44
- 230000000694 effects Effects 0.000 abstract description 14
- 230000007704 transition Effects 0.000 abstract description 12
- 238000005090 crystal field Methods 0.000 abstract description 7
- ZPDRQAVGXHVGTB-UHFFFAOYSA-N gallium;gadolinium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Gd+3] ZPDRQAVGXHVGTB-UHFFFAOYSA-N 0.000 abstract description 7
- 230000005290 antiferromagnetic effect Effects 0.000 abstract description 6
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 5
- 108010053481 Antifreeze Proteins Proteins 0.000 abstract description 4
- 230000005283 ground state Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910052734 helium Inorganic materials 0.000 description 8
- 239000001307 helium Substances 0.000 description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 150000000921 Gadolinium Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000005347 demagnetization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000249931 Doronicum maximum Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- IQGAADOKZGEEQE-LNTINUHCSA-K gadolinium acetylacetonate Chemical compound [Gd+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O IQGAADOKZGEEQE-LNTINUHCSA-K 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- HYBHAIGYQVICOT-UHFFFAOYSA-K gadolinium(3+) perchlorate Chemical compound O=Cl(=O)(=O)O[Gd](OCl(=O)(=O)=O)OCl(=O)(=O)=O HYBHAIGYQVICOT-UHFFFAOYSA-K 0.000 description 1
- SQORATIMOBOFKR-UHFFFAOYSA-H gadolinium(3+);oxalate Chemical compound [Gd+3].[Gd+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O SQORATIMOBOFKR-UHFFFAOYSA-H 0.000 description 1
- VJLSFXQJAXVOEQ-UHFFFAOYSA-N gadolinium(3+);propan-2-olate Chemical compound [Gd+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] VJLSFXQJAXVOEQ-UHFFFAOYSA-N 0.000 description 1
- KGOKDPWKDBWITQ-UHFFFAOYSA-K gadolinium(3+);tribromide Chemical compound Br[Gd](Br)Br KGOKDPWKDBWITQ-UHFFFAOYSA-K 0.000 description 1
- RQXZRSYWGRRGCD-UHFFFAOYSA-H gadolinium(3+);tricarbonate Chemical compound [Gd+3].[Gd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O RQXZRSYWGRRGCD-UHFFFAOYSA-H 0.000 description 1
- DYOBTPTUHDTANY-UHFFFAOYSA-K gadolinium(3+);trifluoromethanesulfonate Chemical compound [Gd+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F DYOBTPTUHDTANY-UHFFFAOYSA-K 0.000 description 1
- ILCLBMDYDXDUJO-UHFFFAOYSA-K gadolinium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Gd+3] ILCLBMDYDXDUJO-UHFFFAOYSA-K 0.000 description 1
- QLAFITOLRQQGTE-UHFFFAOYSA-H gadolinium(3+);trisulfate Chemical compound [Gd+3].[Gd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QLAFITOLRQQGTE-UHFFFAOYSA-H 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- JXJTWJYTKGINRZ-UHFFFAOYSA-J silicon(4+);tetraacetate Chemical compound [Si+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O JXJTWJYTKGINRZ-UHFFFAOYSA-J 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- PKLMYPSYVKAPOX-UHFFFAOYSA-N tetra(propan-2-yloxy)germane Chemical compound CC(C)O[Ge](OC(C)C)(OC(C)C)OC(C)C PKLMYPSYVKAPOX-UHFFFAOYSA-N 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TYIZUJNEZNBXRS-UHFFFAOYSA-K trifluorogadolinium Chemical compound F[Gd](F)F TYIZUJNEZNBXRS-UHFFFAOYSA-K 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Classifications
-
- 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
- H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
- H01F1/017—Compounds
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B21/00—Machines, plants or systems, using electric or magnetic effects
-
- 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
- H01F1/0009—Antiferromagnetic materials, i.e. materials exhibiting a Néel transition temperature
-
- 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
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention discloses a magnetocaloric material, a preparation method and application thereof, and relates to the technical field of magnetic refrigeration, wherein the chemical formula of the magnetocaloric material is Gd 5‑x M 3 O 13.5‑1.5x Wherein x is more than or equal to 0 and less than or equal to 0.335, and M is selected from at least one of Ge and Si. In the present invention, the magnetocaloric material comprises gadolinium, which is a rare earth element and has 8 S 7/2 The magnetic ground state is less influenced by the crystal field, and the orbital angular momentum is close to zero, so that stronger magneto-thermal coupling response is formed; the magnetocaloric material has antiferromagnetic phase transition, magnetic moment is not easy to be quenched by crystal field, large magnetic entropy can be kept near the phase transition temperature, and thermal hysteresis loss and hysteresis loss are small, so that high magnetic entropy utilization rate is kept. The magnetic entropy change of the magnetocaloric material is far higher than that of widely used low-temperature magnetocaloric medium gadolinium gallium garnet Gd 3 Ga 5 O 12 The magnetic entropy change of the air conditioner has good refrigerating effect.
Description
Technical Field
The invention relates to the technical field of magnetic refrigeration, in particular to a magnetocaloric material and a preparation method and application thereof.
Background
Cryogenic zone (0.005-40K) refrigeration technology in hydrogen and helium (including He) 3 ) The method has very important roles in the fields of liquefaction, quantum computation, high-energy physics, superconducting technology, modern space technology and the like. The magnetic refrigeration is a technology for realizing high-efficiency refrigeration by utilizing a magnetocaloric material (a refrigeration working medium material for realizing system temperature change based on a magnetocaloric effect), has high thermal cycle efficiency, small device volume, low microphonic and thermal noise characteristics and great development potential in a low-temperature area. The magnetocaloric effect is the core of magnetic refrigeration technology and its physical description is the external field dependence of the magnetic entropy of the system. Specifically, when a magnetic field is applied to the magnetocaloric material, the magnetic moment thereof tends to be in an ordered state (low entropy state), and when the external field is removed, the magnetic moment of the system returns to an unordered state (high entropy state). The repeated operation of the external field can realize the transition between the low entropy state and the high entropy state, and the heat absorption and release process is accompanied, so that the refrigeration cycle is realized.
The key of the magnetic refrigeration technology is the selection of the magnetic heat material, and the ideal magnetic heat material has the following characteristics: (1) has large magnetic entropy change and high adiabatic temperature change; (2) has a low phonon and electron specific heat; (3) the phase transition temperature should be within the operating temperature window; (4) having as high a heat conduction efficiency as possible; (5) Has low preparation cost, good processing characteristics and good mechanical and chemical corrosion resistance.
In order to realize the integration, miniaturization and multifunctional characteristics of the refrigerating device, the large magnetic entropy change characteristics of the magnetocaloric material not only require that the magnetic entropy change has high quality unit (J.kg) –1 ·K –1 ) Further has a high volume unit (mJ.cm) –3 ·K –1 ). However, the magnetic entropy change of the existing magnetocaloric material in a low temperature area is smaller, particularly the magnetic entropy variable value of volume unit is low, the preparation process is more complex, the cost is high, such as widely used gadolinium gallium garnet Gd 3 Ga 5 O 12 At a magnetic field Δh=9t, the maximum mass unit magnetic entropy change is only 43.4j·kg -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 307.3 mJ.cm -3 ·K -1 The adiabatic temperature was changed to 20K under adiabatic demagnetization conditions (9.4 T.fwdarw.0.7T).
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a magnetocaloric material, a preparation method and application thereof, and aims to solve the problem that the magnetic entropy change of the existing magnetocaloric material in a low-temperature region is small.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a magnetocaloric material, wherein the magnetocaloric material has the chemical formula Gd 5- x M 3 O 13.5-1.5x Wherein x is more than or equal to 0 and less than or equal to 0.335, and M is selected from at least one of Ge and Si.
Optionally, the magnetocaloric material belongs to a hexagonal system, and the space group of the magnetocaloric material is P6 3 /m。
Optionally, the chemical formula of the magnetocaloric material is Gd 4.667 Si 3 O 13 、Gd 4.667 (Si y Ge 1-y ) 3 O 13 、Gd 4.667 Ge 3 O 13 、Gd 4.833 Si 3 O 13.250 、Gd 4.833 (Si y Ge 1-y ) 3 O 13.250 、Gd 4.833 Ge 3 O 13.250 、Gd 5 Si 3 O 13.5 、Gd 5 (Si y Ge 1-y ) 3 O 13.5 Or Gd 5 Ge 3 O 13.5 Wherein y is more than 0 and less than 1.
In a second aspect of the present invention, there is provided a method for preparing a magnetocaloric material according to the present invention as described above, comprising the steps of:
mixing a gadolinium source with an M source to obtain a mixture;
carrying out heat treatment on the mixture at a preset temperature for a preset time to obtain the magnetocaloric material;
wherein the M source is selected from at least one of Ge source and Si source.
Optionally, the preset temperature is 900-1300 ℃, and the preset time is 3-30h.
Optionally, the gadolinium source, the M source and the flux are mixed to obtain a mixture.
Optionally, mixing a gadolinium source, an M source and a grinding aid to obtain a mixture;
or mixing gadolinium source, M source, fluxing agent and grinding aid to obtain a mixture.
In a third aspect of the invention, there is provided the use of a magnetocaloric material according to the invention as described above and/or a magnetocaloric material prepared by the preparation method according to the invention as described above in the field of magnetic refrigeration.
Optionally, the application temperature of the magnetocaloric material is 0.005-40K.
In a fourth aspect of the present invention, there is provided a magnetic refrigeration apparatus comprising a magnetocaloric material according to the present invention and/or a magnetocaloric material prepared by the preparation method according to the present invention.
The beneficial effects are that: in the present invention, the magnetocaloric materialComprises gadolinium (Gd) which is a rare earth element and has 8 S 7/2 The magnetic ground state is less influenced by the crystal field, and the orbital angular momentum is close to zero, so that strong magneto-thermal coupling response is formed. The magnetocaloric material has antiferromagnetic characteristic, magnetic moment is not easy to quench by crystal field, large magnetic entropy can be kept near phase transition temperature (spin sequence phase transition temperature is in the range of 0.005-0.4K temperature zone), and thermal hysteresis loss and hysteresis loss of the system are small, so that higher magnetic entropy utilization rate is kept. In the invention, when the delta H is 8.9 or 9T, the maximum mass unit magnetic entropy change of the magnetocaloric material is more than 70 J.kg -1 ·K -1 The magnetic entropy change of the corresponding volume unit exceeds 500 mJ.cm -3 ·K -1 The maximum adiabatic temperature change of the magnetocaloric material is more than 30K and is far higher than that of widely used low-temperature magnetocaloric medium gadolinium gallium garnet Gd 3 Ga 5 O 12 The magnetic entropy change of (DeltaH was 9T, and the highest mass unit magnetic entropy became 43.4 J.kg) -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 307.3 mJ.cm -3 ·K -1 ) And the maximum adiabatic temperature change has good refrigeration effect.
Drawings
FIG. 1 shows Gd in example 1 of the present invention 4.667 Si 3 O 13 X-ray diffraction test result diagram of (c).
FIG. 2 shows Gd in example 2 of the present invention 4.833 Si 3 O 13.250 X-ray diffraction test result diagram of (c).
FIG. 3 shows Gd in example 1 of the present invention 4.667 Si 3 O 13 A magnetic susceptibility curve between 0.4 and 300K.
FIG. 4 shows Gd in example 2 of the present invention 4.833 Si 3 O 13.250 A magnetic susceptibility curve between 2 and 300K.
FIG. 5 shows Gd in example 1 of the present invention 4.667 Si 3 O 13 Heat capacity curves at different external fields.
FIG. 6 shows Gd in example 1 of the present invention 4.667 Si 3 O 13 Magnetic entropy curves at different external fields and temperatures.
FIG. 7 shows Gd in example 2 of the present invention 4.833 Si 3 O 13.250 Magnetic entropy curves at different external fields and temperatures.
Detailed Description
The invention provides a magnetocaloric material, a preparation method and application thereof, and the invention is further described in detail below for making the purpose, technical scheme and effect of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Gadolinium gallium garnet Gd 3 Ga 5 O 12 Is a widely used low Wen Cire working medium, and when the temperature is lower than 5K, the highest mass unit magnetic entropy of the working medium under the external field of delta H=9T is changed into 43.4J.kg -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 307.3 mJ.cm -3 ·K -1 The adiabatic temperature under the adiabatic demagnetization condition (9.4T-0.7T) is changed into 20K, the magnetic entropy change of the material in a low temperature area is smaller, and the refrigerating effect of the material needs to be further improved. Based on the above, the embodiment of the invention provides a magnetocaloric material, wherein the chemical formula of the magnetocaloric material is Gd 5-x M 3 O 13.5-1.5x Wherein x is more than or equal to 0 and less than or equal to 0.335, and M is selected from at least one of Ge and Si.
In an embodiment of the invention, the magnetocaloric material comprises gadolinium (Gd), a rare earth element, having 8 S 7/2 The magnetic ground state is less influenced by the crystal field, and the orbital angular momentum is close to zero, so that strong magneto-thermal coupling response is formed. The magnetocaloric material has antiferromagnetic behavior, easy magnetic moment overturning, high magnetic entropy keeping near the phase transition temperature (spin sequence phase transition temperature is in the range of 0.005-0.4K temperature zone), and low system thermal hysteresis loss and hysteresis loss, thereby keeping high magnetic entropy utilization rate. In this embodiment, when ΔH is 8.9 or 9T, the maximum mass unit magnetic entropy of the magnetocaloric material is greater than70J·kg -1 ·K -1 The magnetic entropy change of the corresponding volume unit exceeds 500 mJ.cm -3 ·K -1 The maximum adiabatic temperature change of the magnetocaloric material is more than 30K and is far higher than that of gadolinium gallium garnet Gd 3 Ga 5 O 12 The magnetic entropy change and the adiabatic temperature change of the air conditioner have good refrigeration effect.
In addition, in the embodiment of the invention, the magnetocaloric material has the processing characteristics of high mechanical stability, oxidation resistance and easy granulation; the magnetocaloric material has low lattice and electron specific heat, small debye heat capacity coefficient and low internal heat load loss in the operation external field cycle; the magnetocaloric material also has the property of an insulator, has higher low temperature heat conduction, is favorable for heat transmission and heat balance in magnetization-demagnetization circulation, and is not easy to form vortex; the phase transition temperature of the magnetocaloric material is 0.005-0.4K, and when the magnetocaloric material is near the magnetically ordered temperature, the temperature change formed by magnetizing-demagnetizing the magnetocaloric material is the largest.
Therefore, the magnetocaloric material provided by the embodiment of the invention has large magnetic entropy change (the magnetic entropy variable value is obviously higher than that of the magnetocaloric working medium widely used at present) in a low temperature area, the refrigerating capacity is large, the adiabatic temperature change value is high, and a good refrigerating effect can be realized in the low temperature area. In addition, the magnetic entropy variable value of the volume unit of the magnetocaloric material is high, and the magnetic refrigerating device with high integration, miniaturization and multifunctional characteristics is favorable to be developed.
In some embodiments, the magnetocaloric material belongs to the hexagonal system, and the space group is P6 3 And/m. Wherein Gd 3+ Has structural randomness at the 4h site, and Gd in the magnetocaloric material with the configuration 3+ Can form magnetic clusters, induce ferromagnetic polarization field, thereby promoting Gd 3+ The magnetic moment of the sub-lattice is inverted, and the enhancement of the magneto-thermal coupling response is realized.
In some embodiments, the chemical formula of the magnetocaloric material includes, but is not limited to, gd 4.667 Si 3 O 13 、Gd 4.667 (Si y Ge 1-y ) 3 O 13 、Gd 4.667 Ge 3 O 13 、Gd 4.833 Si 3 O 13.250 、Gd 4.833 (Si y Ge 1-y ) 3 O 13.250 、Gd 4.833 Ge 3 O 13.250 、Gd 5 Si 3 O 13.5 、Gd 5 (Si y Ge 1-y ) 3 O 13.5 Or Gd 5 Ge 3 O 13.5 Wherein y is more than 0 and less than 1. Illustratively, when the magnetocaloric material has the chemical formula Gd 4.667 (Si y Ge 1-y ) 3 O 13 In particular Gd 4.667 (Si 0.5 Ge 0.5 ) 3 O 13 、Gd 4.667 (Si 0.3 Ge 0.7 ) 3 O 13 Etc.; when the chemical formula of the magnetocaloric material is Gd 4.833 (Si y Ge 1-y ) 3 O 13.250 In particular Gd 4.833 (Si 0.2 Ge 0.8 ) 3 O 13.250 、Gd 4.833 (Si 0.4 Ge 0.6 ) 3 O 13.250 Etc.; when the chemical formula of the magnetocaloric material is Gd 5 (Si y Ge 1-y ) 3 O 13.5 In particular Gd 5 (Si 0.5 Ge 0.5 ) 3 O 13.5 、Gd 5 (Si 0.7 Ge 0.3 ) 3 O 13.5 Etc.
In some embodiments, the magnetocaloric material has the formula Gd 4.667 Si 3 O 13 Its debye lattice heat capacity coefficient α=9.0×10 -5 Has low phonon and electron specific heat. When the magnetic field change Δh=8.9t, the highest mass unit magnetic entropy becomes 78.2j·kg -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 506.7 mJ.cm -3 ·K -1 The maximum adiabatic temperature becomes 31.5K.
The embodiment of the invention also provides a preparation method of the magnetocaloric material, which comprises the following steps:
s1, mixing a gadolinium source and an M source to obtain a mixture;
s2, carrying out heat treatment on the mixture at a preset temperature for a preset time to obtain the magnetocaloric material;
wherein the M source is selected from at least one of Ge source and Si source.
The preparation method provided by the embodiment of the invention has the advantages of simple process, convenient operation and high yield, is favorable for realizing large-scale production of the magnetocaloric material, and can be used for preparing the magnetocaloric material which has large magnetic entropy change in a low-temperature region, high adiabatic temperature change value and good refrigeration effect in the low-temperature region. In addition, the prepared magnetocaloric material also has the processing characteristics of high mechanical stability, oxidation resistance and easy granulation, and has good application prospect.
In step S1, in some embodiments, the gadolinium source includes, but is not limited to, at least one of gadolinium oxide, inorganic gadolinium salts, organic gadolinium salts, gadolinium boride.
In some specific embodiments, the inorganic gadolinium salt includes, but is not limited to, at least one of gadolinium fluoride, gadolinium chloride, gadolinium bromide, gadolinium nitrate, gadolinium sulfate, gadolinium perchlorate, gadolinium hydroxide, gadolinium carbonate.
In some specific embodiments, the organic gadolinium salt includes, but is not limited to, at least one of gadolinium oxalate, gadolinium triflate, gadolinium acetylacetonate, gadolinium isopropoxide.
In some embodiments, the silicon source (Si source) includes, but is not limited to, at least one of silicon oxide, silicon acetate, tetraethyl silicate, amorphous silicon.
In some embodiments, the germanium source (Ge source) includes, but is not limited to, at least one of germanium dioxide, germanium tetrachloride, germanium isopropoxide.
The raw materials (including gadolinium source, silicon source and germanium source) have low cost, wide sources and good processing characteristics, and are beneficial to industrialized popularization.
In some embodiments, the gadolinium source, the M source, and the flux are mixed to obtain a mixture. In the embodiment, the addition of the fluxing agent is beneficial to accelerating the heat treatment process and promoting the mass transfer effect, thereby being beneficial to the full reaction of the raw materials in the heat treatment process and reducing the reaction temperature and the cost.
In some specific embodiments, the fluxing agent includes, but is not limited to, at least one of lithium sulfate, sodium sulfate, potassium sulfate, sodium chloride, potassium chloride.
In some embodiments, the gadolinium source, the M source, and the grinding aid are mixed to obtain a mixture. In the embodiment, the addition of the grinding aid is beneficial to the thorough mixing of the gadolinium source and the M source and the full reaction of raw materials in the subsequent heat treatment process, so that the processing characteristics of the product are improved. In some specific embodiments, the grinding aid includes, but is not limited to, at least one of ethylene glycol, oleic acid.
In some embodiments, the gadolinium source, the M source, and the fluxing agent, the grinding aid are mixed to provide a mixture.
In some embodiments, the means of mixing includes, but is not limited to, stirring mixing or ball milling mixing. In particular, the means of mixing includes, but is not limited to, one of a ball mill, a blender or a mixer.
In some embodiments, the mixing is for a period of 0.5 to 12 hours. For example, 0.5h, 2h, 5h, 10h, 12h, or the like can be used.
In some embodiments, according to Gd 5-x M 3 O 13.5-1.5x The gadolinium source and the M source are mixed according to the stoichiometric ratio of each element, so as to obtain a mixture.
In step S2, in some embodiments, the preset temperature is 900-1300 ℃, for example, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, or 1300 ℃; the preset time is 3-30h, and can be 3h, 4h, 5h, 7h, 9h, 10h, 15h, 19h, 20h, 25h or 30h, for example.
In some embodiments, the heat treatment apparatus includes, but is not limited to, a muffle furnace, a tube furnace, or an arc furnace.
The embodiment of the invention also provides application of the magnetocaloric material in the field of magnetic refrigeration.
The embodiment of the invention also provides an application of the magnetocaloric material prepared by the preparation method in the field of magnetic refrigeration.
The embodiment of the invention also provides the magnetocaloric material and the application of the magnetocaloric material prepared by the preparation method in the field of magnetic refrigeration.
In some embodiments, the magnetocaloric material has an application temperature of 0.005 to 40K. In the embodiment, the magnetocaloric material has obvious heat absorption and release effects in a temperature range of 0.005-40K, and has a higher application temperature range. The application temperature of the magnetocaloric material may be, for example, 0.005K, 0.1K, 2K, 4K, 20K, 25K or 40K. The phase transition temperature (0.005-0.4K) of the magnetocaloric material is lower than the helium liquefaction point (4.2K), so that the magnetocaloric material not only can realize the magnetic liquefaction of helium, but also can replace He 3 Dilution refrigeration, i.e. the application temperature zone of the magnetocaloric material contains helium (including He 3 ) And the liquefaction temperature of hydrogen, therefore, the application of the magnetocaloric material is beneficial to realizing the efficient magnetic liquefaction of helium and hydrogen. In addition, the magnetocaloric material has a great application prospect in the fields of quantum computation, high-energy physics, superconducting technology, modern space technology and the like.
The embodiment of the invention also provides a magnetic refrigeration device, which comprises the magnetocaloric material disclosed by the embodiment of the invention, or comprises the magnetocaloric material prepared by adopting the preparation method disclosed by the embodiment of the invention, or comprises the magnetocaloric material disclosed by the embodiment of the invention and the magnetocaloric material prepared by adopting the preparation method disclosed by the embodiment of the invention. In the embodiment, the magnetic refrigeration device has good refrigeration effect in a temperature range of 0.005-40K, good refrigeration capacity in the temperature range of 0.005-40K, high cycle efficiency and no pollution. The magnetic refrigeration device provided in this embodiment may operate in a carnot cycle or stirling cycle mode, in He 3 The substitution, helium and hydrogen magnetic liquefaction fields have wide application prospects. In addition, the magnetic refrigeration device can be used for cascade liquid-free helium 2K refrigeration; it can also be used for cooling superconducting coils to improve signal-to-noise ratio and resolving power of magnetic resonance apparatus (MRI), etc.
In this embodiment, the magnetic refrigeration device has a good refrigeration effect in a low temperature region, and has a compact structure and high integration.
The following is a detailed description of specific examples.
Example 1
The present embodiment provides a magnetocaloric material having the chemical formula Gd 4.667 Si 3 O 13 。
The preparation method of the magnetocaloric material comprises the following steps:
gd is put into 2 O 3 SiO (silicon oxide) 2 Placing into a ball mill at a molar ratio of 0.7778:1, and adding Gd 2 O 3 With SiO 2 5% of glycol by mass and ball milling for 1h to obtain a mixture;
the mixture is put into a muffle furnace and annealed for 15 hours at 1100 ℃ to obtain Gd 4.667 Si 3 O 13 Is a magnetocaloric material of (a).
Example 2
The present embodiment provides a magnetocaloric material having the chemical formula Gd 4.833 Si 3 O 13.250 。
The preparation method of the magnetocaloric material comprises the following steps:
gd is put into 2 O 3 SiO (silicon oxide) 2 Placing in a ball mill at a molar ratio of 0.8055:1, and adding Gd 2 O 3 With SiO 2 5% of glycol by mass and ball milling for 3 hours to obtain a mixture;
the mixture is put into a muffle furnace and annealed for 15 hours at 1300 ℃ to obtain Gd 4.833 Si 3 O 13.250 Is a magnetocaloric material of (a).
And (3) testing:
(1) For the magnetocaloric materials of examples 1 and 2 (Gd, respectively 4.667 Si 3 O 13 And Gd 4.833 Si 3 O 13.250 ) X-ray diffraction test (wavelength used)) And Rietveld refinement was performed, the results are shown in fig. 1 and 2, respectively. As can be seen from fig. 1, gd 4.667 Si 3 O 13 Pure phase of the product, goodness of fit R p ＝1.64，R wp ＝2.32，χ 2 = 4.405. In addition, gd 4.667 Si 3 O 13 The diffraction peak shape is sharp and the crystallization degree is high.
As can be seen from fig. 2, gd 4.833 Si 3 O 13.250 Pure phase of the product, goodness of fit R p ＝1.73，R wp ＝2.38，χ 2 = 2.207. In addition, gd 4.833 Si 3 O 13.250 The diffraction peak shape is sharp and the crystallization degree is high.
By measuring Gd 4.667 Si 3 O 13 And Gd 4.833 Si 3 O 13.25 Belonging to hexagonal system, the space groups are all P6 3 And/m. Wherein Gd 4.667 Si 3 O 13 The unit cell parameters of (2) areα＝β＝90°，γ＝120°。
(2) The magnetocaloric materials of examples 1 and 2 were tested for their magnetic properties by a combination of Physical Property Measurement System (PPMS) and superconducting quantum interference device (SQUID) magnetometer, in combination with He 3 The ultra-low temperature refrigeration device provides a low temperature environment.
a. Magnetic susceptibility curve:
gd in example 1 4.667 Si 3 O 13 The susceptibility curves between 0.4 and 300K are shown in FIG. 3, where the test external field is 0.1T. From FIG. 3, gd 4.667 Si 3 O 13 Is an antiferromagnetic attribute.
Gd in example 2 4.833 Si 3 O 13.250 The susceptibility curves between 2-300K are shown in FIG. 4, where the test external field is 0.01T. From FIG. 4, gd 4.833 Si 3 O 13.250 Is an antiferromagnetic attribute.
b. Heat capacity curve:
gd in example 1 4.667 Si 3 O 13 The heat capacity curves under different external magnetic fields are shown in fig. 5, wherein the test external magnetic fields (hereinafter referred to as external fields) H are respectively 0T,2T,5T and 8.9T. Analysis of the h=0t curve shows that the specific heat of the system around 2K is expressed as T -2 Dependency, i.e. antiferromagnetically ordered. Debye model fitting to know its phononsSpecific heat parameter α=9.0×10 -5 。
c. Magnetic entropy change curve:
gd in example 1 4.667 Si 3 O 13 The magnetic entropy change curves under different external fields H and temperatures T are shown in FIG. 6, and the analysis of FIG. 6 shows that Gd 4.667 Si 3 O 13 At the external field h=1t, the highest mass unit magnetic entropy becomes 7.5j·kg -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 48.7 mJ.cm -3 ·K -1 The method comprises the steps of carrying out a first treatment on the surface of the When h=3t, the highest mass unit magnetic entropy becomes 40.3j·kg -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 261.2 mJ.cm -3 ·K -1 The method comprises the steps of carrying out a first treatment on the surface of the When h=5t, the highest mass unit magnetic entropy becomes 61.3j·kg -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 397.2 mJ.cm -3 ·K -1 The method comprises the steps of carrying out a first treatment on the surface of the When h=7t, the highest mass unit magnetic entropy becomes 73.5j·kg -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 476.3 mJ.cm -3 ·K -1 The method comprises the steps of carrying out a first treatment on the surface of the When h=8.9t, the maximum mass unit magnetic entropy becomes 78.2j.kg -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 506.7 mJ.cm -3 ·K -1 。
Gd in example 2 4.833 Si 3 O 13.250 The magnetic entropy change curves under different external fields H and temperatures T are shown in FIG. 7, and it can be seen that the maximum mass unit magnetic entropy becomes 7.1 J.kg under the external field H=1T -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 46.0 mJ.cm -3 ·K -1 The method comprises the steps of carrying out a first treatment on the surface of the When h=3t, the highest mass unit magnetic entropy becomes 38.9j·kg -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 252.1 mJ.cm -3 ·K -1 The method comprises the steps of carrying out a first treatment on the surface of the When h=5t, the highest mass unit magnetic entropy becomes 60.5j·kg -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 392.0 mJ.cm -3 ·K -1 The method comprises the steps of carrying out a first treatment on the surface of the When h=7t, the highest mass unit magnetic entropy becomes 73.1j·kg -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 473.7 mJ.cm -3 ·K -1 The method comprises the steps of carrying out a first treatment on the surface of the When h=9t, the maximum mass unit magnetic entropy becomes 78.1j·kg -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 506.1 mJ.cm -3 ·K -1 。
It can be seen that Gd in example 1 of the present invention 4.667 Si 3 O 13 And Gd in example 2 4.833 Si 3 O 13.250 The magnetic entropy change is far better than the commercial magnetic refrigeration working medium gadolinium gallium garnet Gd 3 Ga 5 O 12 (43.4J·kg -1 ·K -1 /307.3mJ·cm -3 ·K -1 )。
The magnetic entropy change is calculated by specific heat test and magnetization test, and concretely, the relation between the magnetic entropy and the specific heat is as follows:
wherein S (H, T) is entropy under the external field H and the temperature T, and the integral upper limit is T f Lower limit T 0 Is 0, C p (H, T) is constant pressure heat capacity under the external field H and the temperature T. -DeltaS m S (H, T) and S (0, T) represent magnetic entropy under the external field H and zero field respectively, namely the magnetic entropy becomes the difference between the entropy of the external field H and the entropy of the zero external field at the same temperature.
The magnetic entropy change can also be obtained from maxwell's equations, approximated as:
wherein M is the magnetization at temperature T and external field H.
d. Maximum adiabatic temperature change, relative refrigeration capacity
The adiabatic temperature change of the magnetocaloric material can be determined by the specific heat test. By determining the isentropic points of the magnetic entropy curve when the external field is H and 0, the theoretical adiabatic temperature change can be calculated. Gd in example 1 4.667 Si 3 O 13 The highest adiabatic temperature change at external fields H of 2T,5T and 8.9T were 18.8K, 28.7K and 31.5K, respectively.
The relative refrigeration capacity RCP of the magnetocaloric working medium can be determined by the following relation:
RCP＝ΔS max δT FWHM
wherein DeltaS max Represents the maximum value of magnetic entropy change under the external field H, delta T FWHM Representing the half-width of the corresponding magnetic entropy change curve. Gd in example 1 4.667 Si 3 O 13 Gd in example 2 4.833 Si 3 O 13.250 The relative refrigeration capacity data under different external field variation conditions are shown in table 1 below. As is clear from Table 1, gd 4.667 Si 3 O 13 The relative refrigerating capacities at the external fields H of 1T, 3T, 5T and 8.9T are 38.2 J.kg respectively -1 、147.8J·kg -1 、288.1J·kg -1 553.7 J.kg -1 ；Gd 4.833 Si 3 O 13.250 The relative refrigerating capacities at the external fields H of 1T, 3T, 5T and 9T are 16.3 J.kg respectively -1 、122.7J·kg -1 、252.4J·kg -1 569.9 J.kg -1 。
Table 1 table of performance parameters of the magnetocaloric materials in examples 1 and 2
In summary, the invention provides a magnetocaloric material, a preparation method and use thereof, and in particular provides a magnetocaloric material which has the advantages of simple preparation method, easily available raw materials and larger magnetic entropy change in a low temperature area, so as to realize better refrigeration cycle in the low temperature area. In the present invention, gd 5-x M 3 O 13.5-1.5x The rare earth gadolinium (Gd) is used as a magnetocaloric material, the magnetocaloric material contains rare earth gadolinium (Gd) which has an isotropic magnetic ground state, is hardly influenced by a crystal field, and has an orbital angular momentum close to zero, so that a strong magnetocaloric coupling response is formed. The magnetocaloric material has antiferromagnetic property, magnetic moment is not easy to be quenched by crystal field, and can maintain large magnetic entropy near phase transition temperature (spin sequence phase transition temperature is in the range of 0.005-0.4K), thermal hysteresis loss and magnetismThe hysteresis loss is small, so that the higher magnetic entropy utilization rate is maintained. In the invention, when the delta H is 8.9 or 9T, the maximum mass unit magnetic entropy change of the magnetocaloric material is more than 70 J.kg -1 ·K -1 The magnetic entropy change of the corresponding volume unit exceeds 500 mJ.cm -3 ·K -1 The maximum adiabatic temperature change of the magnetocaloric material is more than 30K and is far higher than that of widely used low-temperature magnetocaloric medium gadolinium gallium garnet Gd 3 Ga 5 O 12 The magnetic entropy change of (DeltaH was 9T, and the highest mass unit magnetic entropy became 43.4 J.kg) -1 ·K -1 The magnetic entropy of the corresponding volume unit becomes 307.3 mJ.cm -3 ·K -1 ) And the maximum adiabatic temperature change, has good refrigeration effect, and has wide application prospect in the fields of high-efficiency magnetic liquefaction of helium and hydrogen, quantum computation, high-energy physics, superconducting technology, modern space technology and the like.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (9)
1. A magneto-caloric material is characterized in that the chemical formula of the magneto-caloric material is Gd 5-x M 3 O 13.5-1.5x Wherein x is more than or equal to 0 and less than or equal to 0.335, and M is selected from at least one of Ge and Si;
the magnetocaloric material belongs to a hexagonal system, and the space group of the magnetocaloric material is P6 3 /m。
2. The magnetocaloric material of claim 1 having the formula Gd 4.667 Si 3 O 13 、Gd 4.667 (Si y Ge 1-y ) 3 O 13 、Gd 4.667 Ge 3 O 13 、Gd 4.833 Si 3 O 13.250 、Gd 4.833 (Si y Ge 1-y ) 3 O 13.250 、Gd 4.833 Ge 3 O 13.250 、Gd 5 Si 3 O 13.5 、Gd 5 (Si y Ge 1-y ) 3 O 13.5 Or Gd 5 Ge 3 O 13.5 Wherein y is more than 0 and less than 1.
3. A method of preparing a magnetocaloric material according to any of claims 1-2, comprising the steps of:
mixing a gadolinium source with an M source to obtain a mixture;
carrying out heat treatment on the mixture at a preset temperature for a preset time to obtain the magnetocaloric material;
wherein the M source is selected from at least one of Ge source and Si source.
4. A method according to claim 3, wherein the predetermined temperature is 900-1300 ℃, and the predetermined time is 3-30 hours.
5. A method of preparation according to claim 3 wherein the gadolinium source, the M source and the flux are mixed to obtain a mixture.
6. A method of preparation according to claim 3, wherein the gadolinium source, the M source and the grinding aid are mixed to obtain a mixture;
or mixing gadolinium source, M source, fluxing agent and grinding aid to obtain a mixture.
7. Use of a magnetocaloric material according to any one of claims 1 to 2 and/or prepared by a preparation method according to any one of claims 3 to 6 in the field of magnetic refrigeration.
8. The use according to claim 7, wherein the magnetocaloric material has an application temperature of 0.005-40K.
9. A magnetic refrigeration device, characterized by comprising the magnetocaloric material according to any one of claims 1 to 2 and/or the magnetocaloric material prepared by the preparation method according to any one of claims 3 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310567109.2A CN116469632B (en) | 2023-05-18 | 2023-05-18 | Magneto-caloric material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310567109.2A CN116469632B (en) | 2023-05-18 | 2023-05-18 | Magneto-caloric material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116469632A CN116469632A (en) | 2023-07-21 |
| CN116469632B true CN116469632B (en) | 2024-03-08 |
Family
ID=87175510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310567109.2A Active CN116469632B (en) | 2023-05-18 | 2023-05-18 | Magneto-caloric material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116469632B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113963881A (en) * | 2021-09-18 | 2022-01-21 | 上海大学 | Gadolinium-based high-entropy perovskite oxide magnetic refrigeration material and preparation method thereof |
| CN114743747A (en) * | 2022-04-25 | 2022-07-12 | 深圳大学 | Low-temperature region magnetic refrigeration material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170002946A (en) * | 2015-06-30 | 2017-01-09 | 삼성전기주식회사 | Magnetic composite and method of manufacturing the same |
-
2023
- 2023-05-18 CN CN202310567109.2A patent/CN116469632B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113963881A (en) * | 2021-09-18 | 2022-01-21 | 上海大学 | Gadolinium-based high-entropy perovskite oxide magnetic refrigeration material and preparation method thereof |
| CN114743747A (en) * | 2022-04-25 | 2022-07-12 | 深圳大学 | Low-temperature region magnetic refrigeration material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116469632A (en) | 2023-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Brück et al. | Magnetic refrigeration—towards room-temperature applications | |
| Guo et al. | Excellent cryogenic magnetocaloric properties in heavy rare-earth based HRENiGa2 (HRE= Dy, Ho, or Er) compounds | |
| CN114743747B (en) | Low-temperature area magnetic refrigeration material and preparation method and application thereof | |
| Balli et al. | Unusual rotating magnetocaloric effect in the hexagonal ErMn O 3 single crystal | |
| Wang | Magnetic and calorimetric study of the magnetocaloric effect in intermetallics exhibiting first-order magnetostructural transitions | |
| CN112852388B (en) | Low-temperature-region rare earth metal oxide magnetocaloric effect material, and preparation method and application thereof | |
| Zhang et al. | Magnetocaloric effect and critical behavior in ternary equiatomic magnesium compounds REPtMg (RE= Tb, Dy and Ho) | |
| CN104946954B (en) | A kind of MnCoGe base magnetic materials with huge piezocaloric effect and its production and use | |
| CN116469632B (en) | Magneto-caloric material and preparation method and application thereof | |
| CN115240940B (en) | Rare earth alkali metal phosphate and preparation method and application thereof | |
| Huang et al. | Preparation, crystal structure and magnetocaloric properties of Tb 5 (Si x Ge 4− x) | |
| Gschneidner Jr et al. | Magnetic refrigeration | |
| CN107910151B (en) | A kind of non-magnetic refrigeration material KBBFO and its preparation method and application | |
| CN113113202B (en) | Magnetocaloric material and preparation method and application thereof | |
| Fujieda et al. | Control of Working Temperature of Large Isothermal Magnetic Entropy Change in La (FexTMySi1− x− y) 13 (TM= Cr, Mn, Ni) and La1− zCez (FexMnySi1− x− y) 13 | |
| Sun et al. | Magnetic properties and magnetocaloric effects of Tm1–x Er x CuAl (x= 0.25, 0.5, and 0.75) compounds | |
| CN108754606A (en) | A kind of CrBr with magnetothermal effect3Monocrystalline and its preparation method and application | |
| Wang et al. | Low-temperature large magnetocaloric effect in the antiferromagnetic ErNi0. 6Cu0. 4Al compound | |
| Xu et al. | Magnetocaloric effect in ErSi compound | |
| Jin et al. | Hysteresis loss and field dependence of magnetic entropy change of Zn-doped Mn5Ge3 system | |
| Xu et al. | Giant low-field magnetocaloric effect in unstable antiferromagnetic Tm1–xErxNi2Si2 (x= 0.2, 0.4) compounds | |
| CN117275863A (en) | Low-temperature magnetic refrigeration material and preparation method and application thereof | |
| CN117448964A (en) | Rare earth alkali metal germanate crystal, synthesis method thereof and application thereof in magnetic refrigeration | |
| Hu et al. | Nearly constant magnetic entropy change involving two closely spaced transitions in the compound LaFe11. 375Al1. 625 | |
| CN115557513B (en) | Gadolinium-based borate compound, preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |