CN111072063A - Perovskite rare earth metal oxide low-temperature magnetic refrigeration material and preparation method thereof - Google Patents
Perovskite rare earth metal oxide low-temperature magnetic refrigeration material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a perovskite rare earth metal oxide low-temperature magnetic refrigeration material and a preparation method thereof, wherein the chemical formula of the perovskite rare earth metal oxide low-temperature magnetic refrigeration material is EuTi1‑xAlxO3Wherein x is 0.05-0.15. The invention relates to a perovskite rare earth metal oxide low-temperature magnetic refrigeration material and a preparation method thereof, wherein aluminum ions (Al) are used for preparing the perovskite rare earth metal oxide low-temperature magnetic refrigeration material3+) Substituted for Ti4+Ions influence the super exchange effect of Ti in 3d state to realize the conversion of antiferromagnetism to ferromagnetism, and synthesize the magnetic refrigeration material with maximum magnetic entropy change value larger than 14J/kg K and refrigeration capacity larger than 50J/kg in the liquid helium temperature region when the magnetic field changes by 1T.
Description
Technical Field
The invention belongs to the technical field of magnetic functional materials, and particularly relates to a perovskite rare earth metal oxide low-temperature magnetic refrigeration material and a preparation method thereof.
Background
Since the perovskite oxide has magnetoresistanceThe magnetic-thermal effect and the spin, charge and orbital freedom degree are related to a series of rich physical properties, so that the magnetic-thermal effect of the perovskite rare earth metal oxide is explored and optimized, the related physical problems are clarified, the application field is expanded, and the magnetic-thermal effect and the orbital freedom degree are also one of the hot subjects in the field of rare earth functional materials in the world at present. Materials which are not deficient in phase transition temperature in the low temperature region, such as EuTiO, among the perovskite rare earth oxides which have been found3The phase transition temperature (6K) is near the temperature of liquid helium, and the product shows quantum paraelectric property and G-type antiferromagnetic property, Eu2+Theoretical magnetic moment of (2) is 7.9 muB. Therefore, the material of the class also should be the direction of research on liquid helium temperature zone magnetic refrigeration. The project is based on literature research and experiment finding that the perovskite rare earth metal oxide EuTiO3The liquid helium temperature zone has giant magnetocaloric effect and does not have obvious hysteresis loss and thermal hysteresis loss phenomena. The magnetic structure can be altered by doping to change the unit cell parameters, introduction of roving electrons or oxygen vacancies. In addition, the magnetic phase change can be regulated and controlled by controlling the size of the material: the antiferromagnetic-paramagnetic phase transformation is changed into ferromagnetic-paramagnetic phase transformation, and then the magnetocaloric effect of the material is influenced. Therefore, the present invention aims to regulate Eu2+The exchange effect between ions forms a complete ferromagnetic state, and the magnetic order utilization rate is improved, so that the magnetic thermal effect of the material is improved.
By means of aluminium ions (Al)3+) Substituted for Ti4+Ions influence the super exchange effect of Ti in 3d state to realize the conversion of antiferromagnetism to ferromagnetism, and synthesize the magnetic refrigeration material with maximum magnetic entropy change value larger than 14J/kg K and refrigeration capacity larger than 50J/kg in the liquid helium temperature region when the magnetic field changes by 1T. The method provides theoretical basis and experimental experience for the exploration of magnetic refrigeration materials with large magnetic entropy change and low hysteresis loss in a liquid helium temperature zone, promotes the process of practical development of an energy-saving and environment-friendly magnetic refrigeration technology, and has important scientific value and strategic significance for low-temperature scientific research and aerospace low-temperature application.
Disclosure of Invention
In view of the above, the invention aims to provide a perovskite rare earth metal oxide low-temperature magnetic refrigeration material and a preparation method thereof, wherein aluminum ions (Al) are used for preparing the perovskite rare earth metal oxide low-temperature magnetic refrigeration material3+) Substituted for Ti4+Influence of ionsThe conversion from the antiferromagnetic property to the ferromagnetic state is realized through the super exchange effect of the Ti 3d state, and the magnetic refrigeration material with the maximum magnetic entropy change value larger than 14J/kg K and the refrigeration capacity larger than 50J/kg is synthesized in the liquid helium temperature region when the magnetic field changes by 1T.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a perovskite rare earth metal oxide low-temperature magnetic refrigeration material is characterized in that: the chemical formula of the perovskite rare earth metal oxide low-temperature magnetic refrigeration material is EuTi1-xAlxO3Wherein x is 0.05-0.15.
Preferably, the magnetic entropy change value of the perovskite rare earth metal oxide low-temperature magnetic refrigeration material is 11.6-15.6J/kg K under the change of a magnetic field of 0-1T, and the magnetic refrigeration capacity is 48-58.2J/kg.
The preparation method of the perovskite rare earth metal oxide low-temperature magnetic refrigeration material comprises the following steps:
europium oxide (Eu)2O3) Dissolving in nitric acid (HNO)38mol/L) and stirring for half an hour, and then adding tetrabutyl titanium titanate [ Ti (OC)4H9)4]And aluminum chloride (AlCl)3) Adding into europium nitrate solution according to a certain chemical ratio, stirring for 1 hr, and adding ethylene glycol (C)2H6O2) Adding the metal nitrate serving as a dispersing agent into the metal nitrate according to a molar ratio of 1:1, continuously stirring the mixture until a uniform solution is obtained, and standing the obtained uniform solution in air at 70 ℃ for a period of time to form the required dry gel;
treating the gel obtained in the step 1 in air at 400 ℃ for 4 hours, then slowly raising the temperature to 800 ℃, and keeping the temperature for 1 hour to remove carbon to obtain a powder material;
annealing the powder material obtained in step 2 at 1100 deg.C for 4 hours in an inert atmosphere to obtain the final EuTi1- xAlxO3A material.
Preferably, in the step 3, the inert atmosphere is 8% of H2And 92% Ar.
Compared with the prior art, the perovskite rare earth metal oxide low-temperature magnetic refrigeration material and the preparation method thereof have the following advantages:
(1) the invention relates to a perovskite rare earth metal oxide low-temperature magnetic refrigeration material and a preparation method thereof, wherein aluminum ions (Al) are used for preparing the perovskite rare earth metal oxide low-temperature magnetic refrigeration material3+) Substituted for Ti4+Ions influence the super exchange effect of Ti in 3d state to realize the conversion of antiferromagnetism to ferromagnetism, and synthesize the magnetic refrigeration material with maximum magnetic entropy change value larger than 14J/kg K and refrigeration capacity larger than 50J/kg in the liquid helium temperature region when the magnetic field changes by 1T.
(2) The perovskite rare earth metal oxide low-temperature magnetic refrigeration material and the preparation method thereof provided by the invention provide theoretical basis and experimental experience for the exploration of the magnetic refrigeration material with large magnetic entropy change and low hysteresis loss in a liquid helium temperature zone, promote the process of practical development of an energy-saving and environment-friendly magnetic refrigeration technology, and have important scientific value and strategic significance for low-temperature scientific research and aerospace low-temperature application.
Drawings
FIG. 1 is an X-ray diffraction pattern of samples of examples 1-3;
FIG. 2 is (a) thermomagnetic curves of ZFC and ZFC at 0.01T magnetic field for samples of examples 1-3; the inset is an enlarged view and a differential curve of the thermomagnetic curve, (b) is a curies fit, the inverse of the magnetic susceptibility varies with temperature;
FIG. 3 is (a) an isothermal magnetization curve at 2-8K for the samples of examples 1-3 under a 0-5T magnetic field variation and (b) an Arrott plot at 2,3,4,5K for the samples of examples 1-3;
FIG. 4 is (a-c) the dependence of the magnetic entropy change on the temperature for the samples of examples 1-3 under different magnetic field changes, (d) the dependence of the magnetic entropy change on the temperature for the samples of examples 1-3 under a 1T magnetic field change, (e) the isothermal magnetization curve for the samples of examples 1-3 under 2K, and (f) the magnetic refrigeration capacity for the samples of examples 1-3 under 1T and 2T magnetic field changes.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention is described in detail below with reference to embodiments and the accompanying drawings.
Comparative examples
Europium oxide (Eu)2O3) Dissolving in nitric acid (HNO)38mol/L) and stirring for half an hour, and then adding tetrabutyl titanium titanate [ Ti (OC)4H9)4]According to the formula EuTiO3The element ratio in (1) was added to the europium nitrate solution and stirred for 1 hour, followed by adding ethylene glycol (C)2H6O2) Adding the metal nitrate as a dispersing agent in a molar ratio of 1:1, stirring the mixture until a uniform solution is obtained, and standing the uniform solution in air at 70 ℃ for a period of time to form the desired dry gel. The resulting gel was treated in air at 400 ℃ for 4 hours, and then the temperature was slowly raised to 800 ℃ and maintained for 1 hour to remove carbon, to obtain a powdery material. The resulting powder material was placed in an inert atmosphere (8% H) at 1100 deg.C2And 92% Ar) for 4 hours to obtain the final EuTiO3A material.
Example 1
Europium oxide (Eu)2O3) Dissolving in nitric acid (HNO)38mol/L) and stirring for half an hour, and then adding tetrabutyl titanium titanate [ Ti (OC)4H9)4]And aluminum chloride (AlCl)3) According to the chemical formula EuTi0.95Al0.05O3The element ratio in (1) was added to the europium nitrate solution and stirred for 1 hour, followed by adding ethylene glycol (C)2H6O2) Adding the metal nitrate as a dispersing agent in a molar ratio of 1:1, stirring the mixture until a uniform solution is obtained, and standing the uniform solution in air at 70 ℃ for a period of time to form the desired dry gel. Will obtainThe gel was treated in air at 400 ℃ for 4 hours, and then the temperature was slowly raised to 800 ℃ and maintained for 1 hour to remove carbon, resulting in a powdery material. The resulting powder material was placed in an inert atmosphere (8% H) at 1100 deg.C2And 92% Ar) for 4 hours to obtain the final EuTi0.95Al0.05O3A material.
Example 2
Europium oxide (Eu)2O3) Dissolving in nitric acid (HNO)38mol/L) and stirring for half an hour, and then adding tetrabutyl titanium titanate [ Ti (OC)4H9)4]And aluminum chloride (AlCl)3) According to the chemical formula EuTi0.9Al0.1O3The element ratio in (1) was added to the europium nitrate solution and stirred for 1 hour, followed by adding ethylene glycol (C)2H6O2) Adding the metal nitrate as a dispersing agent in a molar ratio of 1:1, stirring the mixture until a uniform solution is obtained, and standing the uniform solution in air at 70 ℃ for a period of time to form the desired dry gel. The resulting gel was treated in air at 400 ℃ for 4 hours, and then the temperature was slowly raised to 800 ℃ and maintained for 1 hour to remove carbon, to obtain a powdery material. The resulting powder material was placed in an inert atmosphere (8% H) at 1100 deg.C2And 92% Ar) for 4 hours to obtain the final EuTi0.9Al0.1O3A material.
Example 3
Europium oxide (Eu)2O3) Dissolving in nitric acid (HNO)38mol/L) and stirring for half an hour, and then adding tetrabutyl titanium titanate [ Ti (OC)4H9)4]And aluminum chloride (AlCl)3) According to the chemical formula EuTi0.85Al0.15O3The element ratio in (1) was added to the europium nitrate solution and stirred for 1 hour, followed by adding ethylene glycol (C)2H6O2) Adding the metal nitrate as a dispersing agent in a molar ratio of 1:1, stirring the mixture until a uniform solution is obtained, and standing the uniform solution in air at 70 ℃ for a period of time to form the desired dry gel. The resulting gel was treated in air at 400 ℃ for 4 hours, and thenThe temperature was slowly raised to 800 ℃ and held for 1 hour to remove carbon, yielding a powdered material. The resulting powder material was placed in an inert atmosphere (8% H) at 1100 deg.C2And 92% Ar) for 4 hours to obtain the final EuTi0.85Al0.15O3A material.
The samples obtained in comparative example and examples 1 to 3 were compared and analyzed for the results shown in FIGS. 1 to 4.
Description of the test apparatus: euti1-xAlxO3The structure is measured at room temperature by X-ray of Cu K α ray, and magnetization measurement is carried out by SQUID, and the superconducting quantum interferometer is from MPMS-7 model of Quantum design, Inc.
FIG. 1 is a sample EuTi obtained in examples 1 to 31-xAlxO3(X ═ 0.05,0.1,0.15) X-ray diffraction pattern. The test results showed that the obtained sample was single-phase EuTi1-xAlxO3No diffraction peaks of other impurities were observed, such as: eu (Eu)2Ti2O7,Eu2O3Alumina and TiO2. From EuTiO3To EuTi0.85Al0.15O3The diffraction peak of the compound was slowly shifted to the right because the radius of aluminum ion was smaller than that of titanium ion.
FIG. 2(a) shows EuTi1-xAlxO3(x ═ 0.05,0.1,0.15) Zero Field Cooling (ZFC) and band Field Cooling (FC) thermomagnetic curves at 0.01T magnetic field. Fig. 2(b) is a curie-weiss fit, the inverse of the magnetic susceptibility as a function of temperature. EuTi can be seen from FIG. 2(a)1-xAlxO3The zero field cooling curve and the band field cooling curve of the compound are reversible, which indicates that no thermal hysteresis phenomenon exists, and the curve is very important for the material in practical application. And the curves show EuTi1-xAlxO3Is ferromagnetic, the differential curve shows that as Ti is gradually replaced by Al, the Curie temperature of the compound is reduced, EuTi0.95Al0.05O3Has a Curie temperature of 4.5K, EuTi0.9Al0.1O3And EuTi0.85Al0.15O3The Curie temperature of (A) is 4K. However, EuTiO3Is an antiferromagnetic material, and the neel temperature of the antiferromagnetic material is 5.7K. It is demonstrated that when a small amount of aluminum is substituted for titanium, the magnetic properties of the material are changed from an antiferromagnetic state to a ferromagnetic state, and the transition temperature decreases as the content of aluminum increases. The effect of spin coupling between Eu ions is greatly influenced by crystal field, and at the same time, EuTiO3The antiferromagnetism is mainly derived from the 3d state superexchange of Eu ions by Ti, which is affected when a small amount of Ti is replaced by Al. Therefore, the antiferromagnetic effect is weakened and the ferromagnetism is enhanced, and the ferromagnetism is exhibited as a whole. On the other hand, as can be seen from FIG. 2(b), we found that the reciprocal magnetic susceptibility (χ) of these compoundsm -1) Obeying Curie-Weis Law chi above 5Km -1＝(T-θp)/Cm. Wherein theta ispIs the paramagnetic Curie temperature, CmIs Curie-Weiss constant, and effective magnetic moment (. mu.)eff) Is determined by CmThe value of (c). In general, the paramagnetic curie temperature of ferromagnetic materials is positive and greater than the curie temperature, while the paramagnetic curie temperature of antiferromagnetic materials is negative. Euti1-xAlxO3(x ═ 0.05,0.1,0.15) paramagnetic curie temperature decreases with increasing Al (θ)p2.8K-1.5K) are positive values, but less than the curie temperature. Thus, it is believed that ferromagnetic coupling coexists with antiferromagnetic coupling in some of the samples, but ferromagnetic coupling dominates relatively. The effective magnetic moment is in a reasonable area (mu-7 +/-1 mu)B) This region is consistent with the effective magnetic moment of the free electron previously reported.
FIG. 3(a) shows isothermal magnetization curves of samples obtained in examples 1-3 at 2-28K under a 0-5T magnetic field variation. The magnetization curve is rapidly enhanced along with the increase of the magnetic field at 2K, the magnetization intensity tends to be saturated when the magnetic field is 1T, and meanwhile, the isothermal magnetization curves under the low field are not mutually staggered when the temperature is lower than the Curie temperature. This phenomenon indicates that EuTi obtained in examples 1 to 31-xAlxO3The sample (x ═ 0.05,0.1,0.15) exhibited ferromagnetism. In addition, when the temperature is at TC<T<The isothermal magnetization curve remains nonlinear in the 12K region, which also demonstratesThe presence of ferromagnetic short range order above the phase transition point is likely due to the presence of some ferromagnetic clusters in the paramagnetic state. However, EuTiO3Is an antiferromagnetic material, which shows that a small amount of Al instead of Ti influences the super exchange of Eu ions through the 3d state of Ti, so that the material is converted from antiferromagnetic to ferromagnetic. In EuTiO3In which both an antiferromagnetic state and a ferromagnetic state exist, but the antiferromagnetic state is dominant and thus exhibits antiferromagnetic properties as a whole. When a part of aluminum replaces titanium, the source of antiferromagnetic property (super exchange of Eu ions through 3d state of Ti) is weakened, and at the same time, the crystal field is changed, so that the ferromagnetic state is gradually dominant, and the whole becomes ferromagnetic. We show the EuTi obtained in examples 1-31-xAlxO3Arrott plot of (x ═ 0.05,0.1,0.15) samples as shown in FIG. 3 (b). According to the Banerjee criterion, if the Arrotplot curve has a negative slope or an obvious inflection point, the compound is represented as first-order phase change; if the Arrott curve has a positive slope, the compound is indicated as a second order phase transition. Euti1-xAlxO3The Arrott curve slope for compound (x ═ 0.05,0.1,0.15) is positive, indicating that the phase transition is a second order phase transition.
And the magnetic entropy change under different magnetic field changes can be calculated according to isothermal magnetization curves under different temperatures by utilizing the Maxwell relation. FIGS. 4(a-c) show EuTi1-xAlxO3(x ═ 0.05,0.1,0.15) magnetic entropy change as a function of temperature under different magnetic field changes. From the graph,. DELTA.S can be observedMMonotonically increasing with increasing applied magnetic field. EuTi at a magnetic field variation of 5T and around the liquid helium temperature0.95Al0.05O3The maximum magnetic entropy change value of the magnetic material is 38.4J/kg K, EuTi0.9Al0.1O3The maximum magnetic entropy change value of the magnetic material is 39.5J/kg K, EuTi0.85Al0.15O3The maximum magnetic entropy change value of (2) is 38.3J/kg K. EuTiO sample comparative to comparative example3Maximum magnetic entropy change (- Δ S)M max)40.3J/kg K, there is a small reduction in the substitution of titanium ions by aluminum ions, probably due to the change in the crystal field and the small amount of Eu3+Caused by the formation of ions. But notably in the presence of a magnetic fieldReduced to 2T, EuTi1- xAlxO3The maximum magnetic entropy change values of the compounds (x ═ 0.05,0.1,0.15) were 11.6J/kg K, 14.5J/kg K and 15.6J/kg K, respectively. Relative to EuTiO3The maximum magnetic entropy change of 9.8J/kg K is greatly improved. The low magnetic field change can be realized by the permanent magnet, and the effect of saving cost is achieved. In particular EuTi in example 30.85Al0.15O3The sample, when the magnetic field variation range is 0-1T, the maximum magnetic entropy change reaches 15.6J/kg K, and is larger than many magnetic refrigeration materials with great potential application value in the same transition temperature and the same magnetic field variation range (1T), such as: TmCuAl, ErMn2Si2And ErRu2Si2And the like. FIG. 4(d) shows EuTi1-xAlxO3(x ═ 0.05,0.1,0.15) magnetic entropy change as a function of temperature under a 1T change in magnetic field. It is obvious that the magnetic entropy change value increases with the increase of the aluminum content when the temperature is lower than 6K, because the aluminum replaces titanium to change the magnetism of the material from anti-ferromagnetism to ferromagnetism, and the magnetic order degree of the material is higher under the condition of low magnetic field. FIG. 4(e) is EuTi1-xAlxO3Isothermal magnetization curves at (x ═ 0.05,0.1,0.15)2K, it is evident that the EuTi of examples 1-3 were observed when the magnetic field was below 1T1-xAlxO3The magnetization of the sample is significantly higher than that of EuTiO of the comparative example3. The cooling capacity is another important parameter for measuring the magnetocaloric effect material and is a measure of how much heat can be transferred in an ideal refrigeration cycle.
Defined as the cooling capacity, where T1And T2Temperature at temperature boundary corresponding to half width of magnetic entropy change curve, RC being half width area of entropy change curve[. By using this method, the magnetic refrigeration capacity of the samples of examples 1-3 under the change of the magnetic field of 1T and 2T was obtained, and the results are shown in FIG. 4 (f). As can be seen from the graph, EuTi increases with the aluminum content1-xAlxO3The refrigerating capacity of the compound gradually increases, EuTi0.85Al0.15O3The refrigeration capacities of the compounds were 58.2 and 119.8J/kg, respectively.
The invention researches EuTiO by replacing part of titanium ions with aluminum ions3The magnetic and magnetocaloric effects change from antiferromagnetic to ferromagnetic through the magnetic base state of a small amount of aluminum ion substitute compounds, the ferromagnetic performance is more obvious along with the increase of the aluminum substitute concentration, and the phase transition temperature is reduced from 5.6K to 4K. EuTi samples obtained in examples 1-31-xAlxO3No thermal hysteresis and hysteresis loss were observed in the compounds (x ═ 0.05,0.1, 0.15). When part of aluminum replaces titanium, the magnetic ground state changes, the source of the antiferromagnetism (Eu ions are subjected to super exchange action of the 3d state of Ti) is weakened, the ferromagnetic state is gradually enhanced and is dominant, the ferromagnetism is generally expressed, and the ferromagnetism is enhanced along with the increase of the aluminum content. The magnetic entropy change under low magnetic field is obviously improved due to the change of the magnetic ground state, particularly the EuTi sample in example 30.85Al0.15O3Under the change of a 1T magnetic field, the magnetic entropy change and the magnetic refrigeration capacity reach the maximum, respectively 15.6J/kg K and 58.2J/kg, and are larger than a plurality of rare earth metal alloy magnetic refrigeration materials with great potential application values under the same transformation temperature and the same magnetic field change range. Aluminum doped EuTi1- xAlxO3The compound has large magnetocaloric effect and high-efficiency refrigerating capacity, and has important application value in low-temperature magnetic refrigeration.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (4)
1. A perovskite rare earth metal oxide low-temperature magnetic refrigeration material is characterized in that: the chemical formula of the perovskite rare earth metal oxide low-temperature magnetic refrigeration material is EuTi1-xAlxO3Wherein x is 0.05-0.15.
2. The perovskite rare earth metal oxide low-temperature magnetic refrigeration material as claimed in claim 1, wherein: the magnetic entropy change value of the perovskite rare earth metal oxide low-temperature magnetic refrigeration material is 11.6-15.6J/kg K under the change of a 0-1T magnetic field, and the magnetic refrigeration capacity is 48-58.2J/kg.
3. The preparation method of the perovskite rare earth metal oxide low-temperature magnetic refrigeration material as claimed in claim 1, which is characterized by comprising the following steps:
step 1, batching:
europium oxide (Eu)2O3) Dissolving in nitric acid (HNO)38mol/L) and stirring for half an hour, and then adding tetrabutyl titanium titanate [ Ti (OC)4H9)4]And aluminum chloride (AlCl)3) Adding into europium nitrate solution according to a certain chemical ratio, stirring for 1 hr, and adding ethylene glycol (C)2H6O2) Adding the metal nitrate serving as a dispersing agent into the metal nitrate according to a molar ratio of 1:1, continuously stirring the mixture until a uniform solution is obtained, and standing the obtained uniform solution in air at 70 ℃ for a period of time to form the required dry gel;
step 2, pretreatment:
treating the gel obtained in the step 1 in air at 400 ℃ for 4 hours, then slowly raising the temperature to 800 ℃, and keeping the temperature for 1 hour to remove carbon to obtain a powder material;
step 3, annealing:
annealing the powder material obtained in step 2 at 1100 deg.C for 4 hours in an inert atmosphere to obtain the final EuTi1-xAlxO3A material.
4. The preparation method of the perovskite rare earth metal oxide low-temperature magnetic refrigeration material according to claim 3, characterized by comprising the following steps: in the step 3, the inert atmosphere is 8 percent of H2And 92% Ar.
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| CN112852388A (en) * | 2020-11-16 | 2021-05-28 | 中国科学院江西稀土研究院 | Low-temperature-region rare earth metal oxide magnetocaloric effect material, and preparation method and application thereof |
| CN114182346A (en) * | 2021-11-15 | 2022-03-15 | 中国科学院江西稀土研究院 | Magnetic refrigeration material ETMNO and preparation method and application thereof |
| CN114182343A (en) * | 2021-11-15 | 2022-03-15 | 中国科学院江西稀土研究院 | Polycrystalline EuTiO3Basic magnetic refrigeration material and preparation method thereof |
| CN114583138A (en) * | 2022-03-18 | 2022-06-03 | 杭州怡莱珂科技有限公司 | Sodium ion carrier-carbon composite powder, self-isolation electrode and preparation method |
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| CN114182343A (en) * | 2021-11-15 | 2022-03-15 | 中国科学院江西稀土研究院 | Polycrystalline EuTiO3Basic magnetic refrigeration material and preparation method thereof |
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