CN117303451A - Superfine samarium-iron composite oxide and preparation method and application thereof - Google Patents
Superfine samarium-iron composite oxide and preparation method and application thereof Download PDFInfo
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- AWWAHRLLQMQIOC-UHFFFAOYSA-N [Fe].[Sm] Chemical compound [Fe].[Sm] AWWAHRLLQMQIOC-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 22
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 150000001216 Samarium Chemical class 0.000 claims abstract description 15
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000004146 energy storage Methods 0.000 claims abstract description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 28
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 28
- 235000010333 potassium nitrate Nutrition 0.000 claims description 14
- 239000004323 potassium nitrate Substances 0.000 claims description 14
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 5
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- LVSITDBROURTQX-UHFFFAOYSA-H samarium(3+);trisulfate Chemical compound [Sm+3].[Sm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LVSITDBROURTQX-UHFFFAOYSA-H 0.000 claims description 4
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 4
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- ICKYUJFKBKOPJT-UHFFFAOYSA-K samarium(3+);tribromide Chemical compound Br[Sm](Br)Br ICKYUJFKBKOPJT-UHFFFAOYSA-K 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910000640 Fe alloy Inorganic materials 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000003917 TEM image Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 229910001172 neodymium magnet Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- PRQMIVBGRIUJHV-UHFFFAOYSA-N [N].[Fe].[Sm] Chemical compound [N].[Fe].[Sm] PRQMIVBGRIUJHV-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000009827 uniform distribution Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001954 samarium oxide Inorganic materials 0.000 description 2
- 229940075630 samarium oxide Drugs 0.000 description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0054—Mixed oxides or hydroxides containing one rare earth metal, yttrium or scandium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention belongs to the technical field of magnet materials, and provides an ultrafine samarium-iron composite oxide, a preparation method and application thereof. The method comprises the following steps: mixing nitrate, samarium salt and ferric salt, and heating to obtain an intermediate substance; and mixing the intermediate substance with alkali metal oxide to obtain the superfine samarium-iron composite oxide. The preparation method has the advantages of short preparation time, simple preparation method, low cost and large-scale preparation, and the method can not introduce new impurities, so that the purity of the obtained product is high. The superfine samarium-iron composite oxide prepared by the method has fine and uniform grain size and high specific surface area, provides a good precursor for preparing samarium-iron alloy, and has wide application prospects in the fields of energy storage, solar cells and the like.
Description
Technical Field
The invention relates to the technical field of magnet materials, in particular to an ultrafine samarium-iron composite oxide and a preparation method and application thereof.
Background
With the wide application of permanent magnet motors in electronic appliances and electric automobiles, how to improve the magnetic performance of permanent magnet motors has become a very critical problem. The magnets currently used for these motors are neodymium-iron-boron magnets, however, since neodymium is a rare earth resource and the cost is increasing, a new material is urgently needed to replace the neodymium-iron-boron magnets. The samarium content in the samarium-iron-nitrogen magnet is lower than the neodymium content in the neodymium-iron-boron magnet, and the theoretical maximum energy product (BH) of the samarium-iron-nitrogen magnet max 472 kJ.m -3 The Curie temperature is as high as 470 ℃, 160 ℃ higher than that of the neodymium-iron-boron magnet, and the oxidation resistance and corrosion resistance of the neodymium-iron-boron magnet are better than those of the neodymium-iron-boron magnet. Therefore, the samarium-iron-nitrogen magnet is used for replacing the neodymium-iron-boron magnet, and has wide application prospect.
The samarium-iron-nitrogen magnet is generally prepared by nitriding samarium-iron alloy. The preparation method of samarium-iron alloy mainly comprises a mechanical alloying method, a rapid quenching method, a hydrogenation disproportionation method, a reduction diffusion method and the like. The reduction diffusion method adopts samarium oxide and ferric oxide as raw materials, omits three process links of pure metal preparation, alloy smelting and steel ingot coarse crushing, and is a very promising preparation technology. However, in the general reduction diffusion process, iron oxide and samarium oxide are also required to be prepared, and the prepared temperature is higher, so that the generated oxide grains are coarser, and the generated samarium-iron alloy grains are larger after reduction diffusion. It is known that the larger the grain size, the lower the coercivity and the poorer the high temperature resistance. Currently, common methods for preparing samarium-iron composite oxides include a solid phase method, a sol-gel method, a hydrothermal method and the like. Wherein the reaction temperature of the sol-gel method and the hydrothermal method is higher than 200 ℃, and the prepared minimum particle size is tens of nanometers; the reaction temperature of the solid phase method is higher than 1200 ℃, so that the generated particle size is coarse (the prepared particle size is in micron order), in addition, the sol-gel method and the hydrothermal method have more raw materials, and the process cost is increased while the generated product is impure. Therefore, the method for preparing the superfine samarium-iron composite oxide is simple, convenient, environment-friendly and pollution-free, and has very important significance.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides an ultrafine samarium-iron composite oxide and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an ultrafine samarium-iron composite oxide, which comprises the following steps:
(1) Mixing nitrate, samarium salt and ferric salt, and heating to obtain an intermediate substance;
(2) And mixing the intermediate substance with alkali metal oxide to obtain the superfine samarium-iron composite oxide.
Preferably, the nitrate salt of step (1) comprises lithium nitrate and potassium nitrate; the molar ratio of the lithium nitrate to the potassium nitrate is 3-7: 3 to 7.
Preferably, the samarium salt in the step (1) is samarium nitrate, samarium chloride, samarium bromide or samarium sulfate, and the ferric salt is ferric nitrate, ferrous nitrate, ferric chloride, ferrous chloride, ferric bromide, ferric sulfate or ferrous sulfate.
Preferably, in the step (1), the mass molar ratio of the nitrate, the samarium salt and the ferric salt is 8-12 g:0.4 to 0.6mmol:0.4 to 0.6mmol.
Preferably, the heating rate of the heating in the step (1) is 4-6 ℃/min, and the target temperature is 140-200 ℃; the heat preservation time after reaching the target temperature is 25-35 min.
Preferably, the alkali metal oxide in step (2) is lithium oxide, sodium peroxide or potassium oxide.
Preferably, the molar ratio of the alkali metal oxide in the step (2) to the samarium salt in the step (1) is 1.4 to 1.6:0.4 to 0.6.
Preferably, the stirring speed of the mixing in the step (2) is 550-650 r/min, and the time is 3-5 min.
The invention also provides the superfine samarium-iron composite oxide obtained by the preparation method.
The invention also provides application of the superfine samarium-iron composite oxide in permanent magnet motors, energy storage or solar batteries.
The beneficial effects of the invention are as follows:
(1) The invention provides a preparation method of an ultrafine samarium-iron composite oxide, which comprises the following steps: mixing nitrate, samarium salt and ferric salt, and heating to obtain an intermediate substance; and mixing the intermediate substance with alkali metal oxide to obtain the superfine samarium-iron composite oxide. The preparation method has the advantages of short preparation time, simple preparation method, low cost and large-scale preparation, and the method can not introduce new impurities, so that the purity of the obtained product is high.
(2) The superfine samarium-iron composite oxide prepared by the method has fine and uniform grain size (the grain size is smaller than 15 nm) and high specific surface area, provides a good precursor for preparing samarium-iron alloy, and has wide application prospects in the fields of energy storage, solar cells and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern (2 theta (°) -2θ (°), density (a.u.) -Intensity (a.u.)))) of the ultra-fine samarium-iron composite oxide and the sintered ultra-fine samarium-iron composite oxide of example 1;
FIG. 2 is a transmission electron micrograph of the ultra-fine samarium-iron composite oxide of example 1;
FIG. 3 is a transmission electron micrograph of the ultra-fine samarium-iron composite oxide of example 2;
FIG. 4 is a transmission electron micrograph of the ultra-fine samarium-iron composite oxide of example 3;
FIG. 5 is a transmission electron micrograph of the ultra-fine samarium-iron composite oxide of example 4.
Detailed Description
The invention provides a preparation method of an ultrafine samarium-iron composite oxide, which comprises the following steps:
(1) Mixing nitrate, samarium salt and ferric salt, and heating to obtain an intermediate substance;
(2) And mixing the intermediate substance with alkali metal oxide to obtain the superfine samarium-iron composite oxide.
In the present invention, the nitrate salt of step (1) comprises lithium nitrate and potassium nitrate; the molar ratio of the lithium nitrate to the potassium nitrate is preferably 3-7: 3 to 7, more preferably 4 to 6:4 to 6, more preferably 4.5 to 5:4.5 to 5.
In the invention, the nitrate in the step (1) is used as a reaction solvent, so that the purpose of reducing the reaction temperature is achieved.
In the invention, the samarium salt in the step (1) is samarium nitrate, samarium chloride, samarium bromide or samarium sulfate, and the ferric salt is ferric nitrate, ferrous nitrate, ferric chloride, ferrous chloride, ferric bromide, ferric sulfate or ferrous sulfate.
In the invention, the mass mole ratio of the nitrate, samarium salt and ferric salt in the step (1) is preferably 8-12 g:0.4 to 0.6mmol:0.4 to 0.6mmol, more preferably 9 to 11g:0.45 to 0.55mmol:0.45 to 0.55mmol, more preferably 9.5 to 10g:0.47 to 0.5mmol:0.47 to 0.5mmol.
In the present invention, the heating rate of the heating in the step (1) is preferably 4 to 6 ℃/min, more preferably 4.5 to 5.5 ℃/min, still more preferably 5 to 5.3 ℃/min; the target temperature is preferably 140 to 200 ℃, more preferably 150 to 190 ℃, still more preferably 160 to 170 ℃; the holding time after reaching the target temperature is preferably 25 to 35 minutes, more preferably 27 to 33 minutes, and still more preferably 28 to 30 minutes.
In the present invention, the alkali metal oxide in the step (2) is lithium oxide, sodium peroxide or potassium oxide.
In the present invention, the molar ratio of the alkali metal oxide of step (2) to the samarium salt of step (1) is preferably 1.4 to 1.6:0.4 to 0.6, more preferably 1.45 to 1.55:0.45 to 0.55, more preferably 1.47 to 1.5:0.47 to 0.5.
In the present invention, the stirring rotation speed of the mixing in the step (2) is preferably 550 to 650r/min, more preferably 570 to 630r/min, and even more preferably 580 to 600r/min; the time is preferably 3 to 5 minutes, more preferably 3.5 to 4.5 minutes, and still more preferably 3.9 to 4 minutes.
In the invention, after the mixing in the step (2), the obtained system is naturally cooled, and then the steps of centrifugation and water washing are sequentially carried out, and the centrifugation and water washing are repeated, and finally the superfine samarium-iron composite oxide is obtained by drying.
In the present invention, the target temperature of natural cooling is preferably 20 to 30 ℃, more preferably 22 to 28 ℃, and even more preferably 23 to 25 ℃; the rotational speed of the centrifugation is preferably 10000 to 15000r/min, more preferably 11000 to 14000r/min, and even more preferably 12000 to 13000r/min; the centrifugation time is preferably 8 to 12 minutes, more preferably 9 to 11 minutes, and still more preferably 9.5 to 10 minutes; the number of repetition is preferably not less than 1, more preferably not less than 2, still more preferably not less than 3; the drying temperature is preferably 50 to 70 ℃, more preferably 55 to 65 ℃, and even more preferably 58 to 60 ℃; the drying time is preferably 10 to 14 hours, more preferably 11 to 13 hours, and still more preferably 12 to 12.5 hours.
The invention also provides the superfine samarium-iron composite oxide obtained by the preparation method.
The invention also provides application of the superfine samarium-iron composite oxide in permanent magnet motors, energy storage or solar batteries.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
10g of nitrate (the nitrate comprises lithium nitrate and potassium nitrate, the molar ratio of the lithium nitrate to the potassium nitrate is 4:6), 0.5mmol of samarium nitrate and 0.5mmol of ferric nitrate are mixed, and the mixture is heated to 150 ℃ at a heating rate of 5 ℃/min and is preserved for 30min, so as to obtain an intermediate substance;
mixing the intermediate substance with 1.5mmol lithium oxide at 600r/min for 4min, naturally cooling the obtained system to 25 ℃ after the mixing, centrifuging for 10min at 13000r/min, washing with water, repeating the steps of centrifuging and washing with water for 2 times, and finally drying at 60 ℃ for 12h to obtain the superfine samarium-iron composite oxide.
And sintering the obtained superfine samarium-iron composite oxide at 800 ℃ to obtain the sintered superfine samarium-iron composite oxide.
The reason why the obtained ultra-fine samarium iron composite oxide was sintered at 800 ℃ is to increase the crystallinity of the oxide, because the ultra-fine samarium iron composite oxide prepared in this example has very fine particles and low crystallinity, and the crystallinity is improved and the grain size is increased after sintering at 800 ℃, which is advantageous for characterizing the purity thereof by XRD.
The ultra-fine samarium iron composite oxide obtained in this example and the sintered ultra-fine samarium iron composite oxide were subjected to X-ray characterization to obtain X-ray diffraction patterns of the ultra-fine samarium iron composite oxide and the sintered ultra-fine samarium iron composite oxide in this example, as shown in fig. 1. As can be seen from FIG. 1, the ultra-fine samarium-iron composite oxide prepared in the present example is sintered at 800℃and compared with a standard PDF card, and SmFeO alone 3 No other impurity phase is generated, i.e. the purity of the product prepared in this example is very high.
The ultra-fine samarium-iron composite oxide obtained in this example was characterized by using a transmission electron microscope, and a transmission electron micrograph of the ultra-fine samarium-iron composite oxide in this example was obtained as shown in fig. 2. As can be seen from FIG. 2, the ultra-fine samarium-iron composite oxide prepared in this example has a fine particle size and a uniform distribution, and has an average size of about 8nm.
Example 2
9g of nitrate (the nitrate comprises lithium nitrate and potassium nitrate, the molar ratio of the lithium nitrate to the potassium nitrate is 4.5:5), 0.47mmol of samarium sulfate and 0.47mmol of ferric sulfate are mixed, and the mixture is heated to 160 ℃ at a heating rate of 4.5 ℃/min and is kept for 28min, so as to obtain an intermediate substance;
mixing the intermediate substance with 1.47mmol sodium peroxide at a rotation speed of 580r/min for 3.5min, naturally cooling the obtained system to 23 ℃ after the mixing, centrifuging for 11min at a rotation speed of 12000r/min, washing with water, repeating the steps of centrifuging and washing with water for 3 times, and finally drying at 55 ℃ for 13h to obtain the superfine samarium-iron composite oxide.
The ultra-fine samarium-iron composite oxide obtained in this example was characterized by using a transmission electron microscope, and a transmission electron micrograph of the ultra-fine samarium-iron composite oxide in this example was obtained as shown in fig. 3. As can be seen from FIG. 3, the ultra-fine samarium-iron composite oxide prepared in this example has a fine particle size and a uniform distribution, and has an average size of about 9nm.
Example 3
11g of nitrate (the nitrate comprises lithium nitrate and potassium nitrate, the molar ratio of the lithium nitrate to the potassium nitrate is 5:5.5), 0.55mmol of samarium chloride and 0.55mmol of ferric chloride are mixed, and the mixture is heated to 170 ℃ at a heating rate of 5.5 ℃/min and is kept for 27min, so as to obtain an intermediate substance;
mixing the intermediate substance with 1.55mmol sodium oxide at 630r/min for 4.5min, naturally cooling the obtained system to 27 ℃ after the mixing, centrifuging for 9.5min at 13000r/min, washing with water, repeating the steps of centrifuging and washing with water for 3 times, and finally drying at 65 ℃ for 11h to obtain the superfine samarium-iron composite oxide.
The ultra-fine samarium-iron composite oxide obtained in this example was characterized by using a transmission electron microscope, and a transmission electron micrograph of the ultra-fine samarium-iron composite oxide in this example was obtained as shown in fig. 4. As can be seen from FIG. 4, the ultra-fine samarium-iron composite oxide prepared in this example has a fine particle size and a uniform distribution, and has an average size of about 10nm.
Example 4
Mixing 12g of nitrate (the nitrate contains lithium nitrate and potassium nitrate, the molar ratio of the lithium nitrate to the potassium nitrate is 5:5), 0.58mmol of samarium nitrate and 0.6mmol of ferrous nitrate, heating to 200 ℃ at a heating rate of 6 ℃/min, and preserving heat for 30min to obtain an intermediate substance;
mixing the intermediate substance with 1.6mmol lithium oxide at 650r/min for 5min, naturally cooling the obtained system to 30 ℃ after the mixing, centrifuging for 8min at 15000r/min, washing with water, repeating the steps of centrifuging and washing with water for 2 times, and finally drying at 70 ℃ for 10h to obtain the superfine samarium-iron composite oxide.
The ultra-fine samarium-iron composite oxide obtained in this example was characterized by using a transmission electron microscope, and a transmission electron micrograph of the ultra-fine samarium-iron composite oxide in this example was obtained as shown in fig. 5. As can be seen from FIG. 5, the ultra-fine samarium-iron composite oxide prepared in this example has a fine particle size and a uniform distribution, and has an average size of about 14nm.
As can be seen from the above examples, the present invention provides an ultrafine samarium iron composite oxide, and a preparation method and an application thereof. The method comprises the following steps: mixing nitrate, samarium salt and ferric salt, and heating to obtain an intermediate substance; and mixing the intermediate substance with alkali metal oxide to obtain the superfine samarium-iron composite oxide. The preparation method has the advantages of short preparation time, simple preparation method, low cost and large-scale preparation, and the method can not introduce new impurities, so that the purity of the obtained product is high. The superfine samarium-iron composite oxide prepared by the method has fine and uniform grain size and high specific surface area, provides a good precursor for preparing samarium-iron alloy, and has wide application prospects in the fields of energy storage, solar cells and the like.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the superfine samarium-iron composite oxide is characterized by comprising the following steps of:
(1) Mixing nitrate, samarium salt and ferric salt, and heating to obtain an intermediate substance;
(2) And mixing the intermediate substance with alkali metal oxide to obtain the superfine samarium-iron composite oxide.
2. The method of claim 1, wherein the nitrate salt of step (1) comprises lithium nitrate and potassium nitrate; the molar ratio of the lithium nitrate to the potassium nitrate is 3-7: 3 to 7.
3. The method of claim 1 or 2, wherein the samarium salt in step (1) is samarium nitrate, samarium chloride, samarium bromide or samarium sulfate, and the iron salt is ferric nitrate, ferrous nitrate, ferric chloride, ferrous chloride, ferric bromide, ferric sulfate or ferrous sulfate.
4. The method of claim 3, wherein the mass molar ratio of nitrate, samarium salt and iron salt in step (1) is 8-12 g:0.4 to 0.6mmol:0.4 to 0.6mmol.
5. The preparation method according to claim 4, wherein the heating rate of step (1) is 4 to 6 ℃/min and the target temperature is 140 to 200 ℃; the heat preservation time after reaching the target temperature is 25-35 min.
6. The method of claim 4 or 5, wherein the alkali metal oxide in step (2) is lithium oxide, sodium peroxide or potassium oxide.
7. The method of claim 6 wherein the molar ratio of the alkali metal oxide of step (2) to the samarium salt of step (1) is from 1.4 to 1.6:0.4 to 0.6.
8. The method according to claim 7, wherein the stirring speed of the mixing in the step (2) is 550-650 r/min for 3-5 min.
9. The ultra-fine samarium-iron composite oxide obtained by the production method according to any one of claims 1 to 8.
10. The use of the ultra-fine samarium-iron composite oxide according to claim 9 in permanent magnet motors, energy storage or solar cells.
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