CN108899146A - A kind of room temperature magnetic refrigerating material and preparation method thereof - Google Patents
A kind of room temperature magnetic refrigerating material and preparation method thereof Download PDFInfo
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- CN108899146A CN108899146A CN201810423706.7A CN201810423706A CN108899146A CN 108899146 A CN108899146 A CN 108899146A CN 201810423706 A CN201810423706 A CN 201810423706A CN 108899146 A CN108899146 A CN 108899146A
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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
- H01F1/012—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
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Abstract
The invention discloses a kind of room temperature magnetic refrigerating materials and preparation method thereof.The chemical constitution formula of the room temperature magnetic refrigerating material is La0.65Sr0.20Gd0.15MnO3.Preparation method is：Reaction raw materials are pressed into La0.65Sr0.20Gd0.15MnO3Atomic stoichionmtry in chemical formula is dissolved in deionized water than weighing, and citric acid is added and ethylene glycol evaporation water forms gel, is sintered and cooled obtained room temperature magnetic refrigerating material La with Muffle furnace after drying and grinding0.65Sr0.20Gd0.15MnO3.The magnetic refrigerating material under 0 ~ 3.0T changes of magnetic field there is biggish magnetic entropy to become（1.12J/kgK）, relative cooling power 215.76J/kg.La prepared by the present invention0.65Sr0.20Gd0.15MnO3Materials chemistry property is stablized, and has excellent magnetothermal effect near room temperature, relative cooling power is big, and preparation method is easy to operate, is suitable for magnetic refrigeration apparatus.
Description
Technical field
The invention belongs to material science and technology fields, are related to a kind of magnetic functional material, and in particular to a kind of room temperature magnetic system
Cold material and preparation method thereof.
Background technique
In recent years, energy and environmental problem is more and more paid attention to, magnetic Refrigeration Technique has gradually come into people's
The visual field.Magnetic refrigeration is a kind of using magnetic material as the Refrigeration Technique of working medium, the basic principle is that by the magnetic thermal effect of magnetic material
It answers（magnetocaloric effect）, i.e. magnetic refrigerating material outwardly releases heat during isothermal magnetization, moves back in insulation
Heat is absorbed from the external world during magnetic, to achieve the effect that refrigeration.Since Brown in 1976 realizes room temperature magnetic with metal Gd
After refrigeration, the research to magnetic material magnetothermal effect is always one of the Important Problems of magnetic fields.Magnetic refrigeration with it is traditional
Vapor compression refrigeration mode is compared, have it is at low cost, it is high-efficient, it is small in size, it is pollution-free, it is noiseless the advantages that, be a kind of great
The refrigeration modes of potentiality.
To room temperature magnetic refrigerating studies have shown that as temperature increases, the Lattice Entropy of magnetic working medium increases, and needs larger magnetic moment
Magnetic material can be only achieved refrigeration purpose.The 4f electronic shell of rare earth element has more unpaired electron, atomic spin magnetic moment
It is larger, there may be biggish magnetothermal effect.Studying more magnetic refrigerating material has：Gd and its compound, perovskite and class calcium
Titanium ore compound, MnFePAs system alloy and various composite materials etc..Wherein perovskite-type compounds purposes is very extensive, is ten
Divide important piezoelectricity ferro material, catalysis material, high temperature superconducting materia and magnetic refrigerating material.Perovskite series compound
Major advantage is that cost substantially reduces compared with Gd and GdSiGe series alloy, and chemical property is stablized, and coercivity is larger.This is
Column compound can regulate and control its Curie temperature to required range by doping, and wherein calcium titanium ore manganose oxide is since it is with larger
Magnetic entropy become, controllable Curie temperature causes the extensive concern of scholars.Calcium titanium ore manganose oxide is applied to grinding for magnetic refrigeration
Study carefully and is published in《Academic research》" Rare Earth Perovskite-Type Manganese Oxides as Magnetic Refrigerant Material " in 2002 has been reported successfully have been prepared at present
Ca-Ti ore type magnetic refrigerating material, the magnetic entropy of many materials gets higher in Gd, but Curie temperature below or is higher than room temperature,
And for magnetic field strength needed for these materials generally in 5T or more, energy consumption is higher.In view of background above, new magnetic material is found
Expect, study hot spot of its magnetism characteristic as international magnetic material research at present, it can be with easy method and lower cost
Prepare can have under the lower magnetic field of near room temperature compared with the magnetic refrigerating material of great magnetic entropy variation and higher relative cooling power at
For the critical issue for needing to solve at present.
The present invention passes through in calcium titanium ore manganose oxide La0.65Sr0.35MnO3Based compound adds Gd element, prepares one kind
Curie temperature near room temperature and under downfield with larger refrigerating capacity material, can be applied to room temperature magnetic refrigerating technology
In.
Summary of the invention
The purpose of the present invention is to provide a kind of operating temperatures near room temperature, has under downfield compared with great magnetic entropy variation,
It can be applied to the room temperature magnetic refrigerating material and preparation method thereof of magnetic Refrigeration Technique.
The chemical constitution formula of room temperature magnetic refrigerating material of the invention is La0.65Sr0.20Gd0.15MnO3。
Prepare above-mentioned room temperature magnetic refrigerating material the specific steps are：
（1）6.5mmol lanthanum salt, 2.0mmol strontium salt, 10mmol manganese salt and 1.5mmol gadolinium salt are weighed, 20 ~ 80mL is added and goes
Citric acid and ethylene glycol is added to being completely dissolved in ionized water, stirring, and wherein the molar ratio of manganese ion and citric acid and ethylene glycol is
1:2:4,70 ~ 95 DEG C are heated to after complete solvent, constant temperature stirs 3 ~ 6h, and evaporation water forms gel, gained gel is placed in
100 ~ 120 DEG C of vacuum oven freeze-day with constant temperature 12 ~ for 24 hours, intermediate product is made.
（2）By step（1）Intermediate product obtained takes out, and after grinding 20 ~ 30min, is fitted into crucible, is then placed in Muffle
Furnace, the pre-burning 2h at 250 ~ 400 DEG C are again heated to 650 ~ 900 DEG C of 8 ~ 10h of Isothermal sinter, cool to room temperature with the furnace, and black is made
Powder is room temperature magnetic refrigerating material La0.65Sr0.20Gd0.15MnO3。
Preferably, the step（1）In lanthanum salt be La (NO3)3·6H2O, strontium salt are Sr (NO3)2, manganese salt Mn
(CH3COO)2·4H2O, gadolinium salt are Gd (NO3)3·6H2O, the crucible are corundum crucible.
The present invention has the following advantages that：
（1）Room temperature magnetic refrigerating material La of the invention0.65Sr0.20Gd0.15MnO3Curie temperature near room temperature, lower
There is the change of biggish magnetic entropy and higher relative cooling power, and preparation method is simple under magnetic field, the cost of raw material is cheap.
（2）Room temperature magnetic refrigerating material La of the invention0.65Sr0.20Gd0.15MnO3Under 0 ~ 3.0T changes of magnetic field, magnetic entropy becomes
Reach as high as 1.87J/ (kgK).
（3）The method of the present invention can repeat to prepare room temperature magnetic refrigerating material La0.65Sr0.20Gd0.15MnO3, which can
Applied in magnetic Refrigeration Technique.
Detailed description of the invention
Fig. 1 is La made from the embodiment of the present invention0.65Sr0.20Gd0.15MnO3Room temperature X ray diffracting spectrum.
Fig. 2 is La made from the embodiment of the present invention0.65Sr0.20Gd0.15MnO3M-T curve.
Fig. 3 is La made from the embodiment of the present invention0.65Sr0.20Gd0.15MnO3 In the magnetic entropy varied curve of near Curie temperature.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and embodiments.
Embodiment：
1）By La0.65Sr0.20Gd0.15MnO3Atomic stoichionmtry in chemical formula is than precise 6.5mmol La (NO3)3·
6H2O、2.0mmol Sr(NO3)2、10mmol Mn(CH3COO)2·4H2O and 1.5mmol Gd (NO3)3·6H220mL is added in O
Deionized water, stirring is to being completely dissolved.Citric acid and ethylene glycol is added, wherein the molar ratio of manganese ion and citric acid and ethylene glycol
It is 1:2:4.It is heated to 90 DEG C until completely dissolved, constant temperature stirs 4h, and evaporation water forms gel, gained gel is placed in 120
Intermediate product is made in DEG C vacuum oven freeze-day with constant temperature 18h.
2）By step（1）Intermediate product obtained takes out, and after grinding 25min with agate mortar, is packed into corundum crucible, is put into
Muffle furnace, the pre-burning 2h at 400 DEG C, it is therefore an objective to organic matter and impurity therein are removed, 750 DEG C of Isothermal sinter 9h are again heated to,
Cool to room temperature with the furnace, obtained black powder is room temperature magnetic refrigerating material La0.65Sr0.20Gd0.15MnO3。
The result that sample made from the present embodiment is measured through X-ray diffractometer is as shown in Figure 1.The result shows that product is
La0.65Sr0.20Gd0.15MnO3Phase structure, belongs to R -3c space group, and cell parameter is respectively a=0.549nm, b=0.549nm, c
=1.340nm, unit cell volume V=0.350nm3。
Pass through the La of MPMS-XL5 type magnetic measurement system measurement0.65Sr0.20Gd0.15MnO3Sample is in magnetic field strength 0.1T
Under magnetic heat（M-T）Curve is as shown in Figure 2.As can be seen from the figure the Curie temperature of sample is 300K.
Pass through MPMS-XL5 type magnetic measurement system measurement this example La0.65Sr0.20Gd0.15MnO3Sample is in Curie's temperature
Spend isothermal magnetization curve nearby（M-H）Curve, and calculate the change of the isothermal magnetic entropy under 0 ~ 3T changes of magnetic field.It calculates
Isothermal magnetic entropy becomes | Δ SM| it is as shown in Figure 3 with the curve of temperature T.Its isothermal magnetic entropy becomes maximum value and reaches 1.87J/ (kgK).And
Calculating the relative cooling power (RCP) in material at 1.0T, 2.0T and 3.0 T is respectively 55.46,104.86 and
215.76 J/kg。
Claims (3)
1. a kind of room temperature magnetic refrigerating material, it is characterised in that the chemical constitution formula of the room temperature magnetic refrigerating material is
La0.65Sr0.20Gd0.15MnO3。
2. a kind of preparation method of room temperature magnetic refrigerating material as described in claim 1, it is characterised in that the specific steps are：
（1）6.5mmol lanthanum salt, 2.0mmol strontium salt, 10mmol manganese salt and 1.5mmol gadolinium salt are weighed, 20 ~ 80mL is added and goes
Citric acid and ethylene glycol is added to being completely dissolved in ionized water, stirring, and wherein the molar ratio of manganese ion and citric acid and ethylene glycol is
1:2:4,70 ~ 95 DEG C are heated to after complete solvent, constant temperature stirs 3 ~ 6h, and evaporation water forms gel, gained gel is placed in
100 ~ 120 DEG C of vacuum oven freeze-day with constant temperature 12 ~ for 24 hours, intermediate product is made；
（2）By step（1）Intermediate product obtained takes out, and after grinding 20 ~ 30min, is fitted into crucible, is then placed in Muffle furnace,
The pre-burning 2h at 250 ~ 400 DEG C is again heated to 650 ~ 900 DEG C of 8 ~ 10h of Isothermal sinter, cools to room temperature with the furnace, and black powder is made
End is room temperature magnetic refrigerating material La0.65Sr0.20Gd0.15MnO3。
3. a kind of preparation method as claimed in claim 2, it is characterised in that the lanthanum salt is La (NO3)3·6H2O, strontium salt are
Sr(NO3)2, manganese salt is Mn (CH3COO)2·4H2O, gadolinium salt are Gd (NO3)3·6H2O, the crucible are corundum crucible.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022148214A1 (en) * | 2021-01-09 | 2022-07-14 | 浙江大学台州研究院 | Method for uniformly doping nanoparticles in high-temperature superconducting material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041472A (en) * | 2007-03-16 | 2007-09-26 | 北京化工大学 | Method for preparing perovskite-like composite metallic oxide by lamina |
| CN103833358A (en) * | 2012-11-21 | 2014-06-04 | 吉林师范大学 | Preparation method of La0.7Ca0.25Sr0.05MnO3 ferromagnetic thin film |
-
2018
- 2018-05-06 CN CN201810423706.7A patent/CN108899146A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041472A (en) * | 2007-03-16 | 2007-09-26 | 北京化工大学 | Method for preparing perovskite-like composite metallic oxide by lamina |
| CN103833358A (en) * | 2012-11-21 | 2014-06-04 | 吉林师范大学 | Preparation method of La0.7Ca0.25Sr0.05MnO3 ferromagnetic thin film |
Non-Patent Citations (1)
| Title |
|---|
| 孔祥宇等: "La0.65Sr0.2Gd0.15MnO3 纳米颗粒的制备及其磁热效应", 《硅酸盐学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022148214A1 (en) * | 2021-01-09 | 2022-07-14 | 浙江大学台州研究院 | Method for uniformly doping nanoparticles in high-temperature superconducting material |
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Application publication date: 20181127 |