CN113744991B - Co2Z type ferrite material and preparation method and application thereof - Google Patents
Co2Z type ferrite material and preparation method and application thereof Download PDFInfo
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- CN113744991B CN113744991B CN202111091418.4A CN202111091418A CN113744991B CN 113744991 B CN113744991 B CN 113744991B CN 202111091418 A CN202111091418 A CN 202111091418A CN 113744991 B CN113744991 B CN 113744991B
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- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
- H01F1/342—Oxides
- H01F1/344—Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4
Abstract
The invention provides a Co 2 Z-type ferrite material and its preparation method and application. The preparation method comprises the following steps: (1) Treating the Y-type mixed solution and the M-type mixed solution by adopting an electrodialysis method to obtain a Y-type cation mixed solution and an M-type cation mixed solution; (3) Respectively mixing the Y-type cation mixed solution and the M-type cation mixed solution with ammonium bicarbonate, and drying to obtain a Y-type ferrite precursor and an M-type ferrite precursor; (4) Carrying out compression molding on the Y-type ferrite precursor, the M-type ferrite precursor and the binder, presintering once, and sintering twice to obtain Co 2 A Z-type ferrite material; the substituted metal ion includes Ba 2+ And/or Sr 2+ . The invention prepares Co with uniform mixing, smaller granularity, less impurities and higher performance by an electrodialysis method 2 The Z-type ferrite material is suitable for ultrahigh frequency magnetic devices, reduces the sintering temperature and saves the preparation process.
Description
Technical Field
The invention belongs to the technical field of magnetic materials, and relates to Co 2 Z-type ferrite material and its preparation method and application.
Background
At present, the demand for miniaturized, portable electronic devices in the ultra-high frequency band is rapidly increasing. The hexagonal ferrite exhibits excellent properties of high magnetic permeability, low loss, and high quality factor at ultra high frequencies. While at room temperature, only Y-type and Co 2 The Z-type and W-type hexagonal ferrites have soft magnetic properties of planar hexagonal ferrites. In view of the materials of the developed antenna elements, the device design requirements of microwave antennas, magneto-optical devices and other electrical equipment still cannot be met. Spinel ferrites exhibit high magnetic permeability, but their cut-off frequency is relatively low and not suitable for frequencies above 0.3 GHz. Co 2 The cut-off frequency fr of the Z-type ferrite material is higher than 1GHz, and the Z-type ferrite material has very high resistivity and great application potential on ultrahigh frequency electronic components. In recent years, co has been improved by improving the formulation and production process 2 The magnetic resonance frequency of Z-type ferrite materials has increased to above 3 GHz.
CN103319165A discloses a Z-type hexaferrite material and a preparation method thereof, wherein the molecular formula of the Z-type hexaferrite material is Sr 3x Ba 3(1-x) Co 2 Gd y Fe 24-y O 41 Or Sr 3x Ba 3(1-x) Co 2 S my Fe 24-y O 41 Wherein 0.4<x<0.6， 0.05<y<0.1; the preparation method comprises the following steps: preparing the raw materials into mixed powder according to a certain weight ratio; wet ball milling the mixed powder, stoving and sievingPre-burning; carrying out secondary wet ball milling on the pre-sintered powder, then carrying out spray granulation, and pressing into a magnetic cake; and sintering the obtained magnetic cake to obtain the Z-shaped hexagonal ferrite. The document adopts a solid-phase reaction method, and the prepared Z-type hexaferrite has a plurality of impure phases and low quality, and the performance of the Z-type hexaferrite is influenced.
CN106587972A discloses a preparation method of Z-type ferrite flake powder, which comprises the following steps: weighing BaCO 3 、Fe 2 O 3 And keeping the temperature of the molten salt at 1150-1200 ℃ for 2-4 h to obtain an M-type ferrite precursor; mixing Fe 2 O 3 And BaCl 2 ·2H 2 Mixing O, adding M-type precursor, and keeping the temperature at 1200-1250 ℃ for 6-10 h to obtain (001) BaFe 12 O 19 Flaky powder; mixing Y-type precursor powder with (001) BaFe 12 O 19 Mixing the flaky powder according to the molar ratio of 1:1, adding molten salt, and keeping the temperature at 1250-1300 ℃ for 6-10 h to obtain Co 2 A Z-type ferrite; the method needs to add extra barium salt when preparing the M-type precursor, and the prepared finished product cannot completely remove the barium salt and has more impurities.
CN106498497A discloses a method for preparing high-purity granular single-crystal Co 2 A method of forming a Z-type ferrite powder, the method comprising: the soluble metal salt is taken as a starting material, and the metal elements are uniformly distributed in the precursor powder by optimizing the dosage and adding mode of the composite precipitator; and then, mixing the precursor with salt, and in the heat treatment process, taking a molten salt liquid phase as an ion transmission medium to accelerate metal ion diffusion in the heat treatment process and promote formation of a target product, and promoting particle growth of the target product to tend to a crystal growth habit through liquid phase growth to show single crystallization. The method has the advantages of complex process flow and difficult component control.
Therefore, how to obtain a ferrite material suitable for ultrahigh frequency devices is a technical problem to be solved urgently.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide Co 2 Z-type ferrite material and preparation method and application thereofUse is provided. The invention prepares Co with uniform mixing, smaller granularity, less impurities and higher magnetic conductivity by an electrodialysis method 2 The Z-type ferrite material is suitable for ultrahigh frequency magnetic devices, reduces the sintering temperature and saves the preparation process.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a Co 2 A method of preparing a Z-type ferrite material, the method comprising the steps of:
(1) Will contain Fe 3+ Soluble metal salt of (2), soluble metal salt containing substituted metal ion, soluble metal salt containing Co 2+ Mixing the soluble metal salt with a solvent to obtain a Y-shaped mixed solution;
will contain Fe 3+ Mixing the soluble metal salt, the soluble metal salt containing the substituted metal ions and the solvent to obtain an M-type mixed solution;
(2) Treating the Y-type mixed solution in the step (1) and the M-type mixed solution in the step (1) respectively by adopting an electrodialysis method to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) Carrying out first mixing on the Y-type cation mixed solution obtained in the step (2) and ammonium bicarbonate, and carrying out first drying to obtain a Y-type ferrite precursor;
carrying out second mixing on the M-type cation mixed solution obtained in the step (2) and ammonium bicarbonate, and carrying out second drying to obtain an M-type ferrite precursor;
(4) Performing compression molding on the Y-type ferrite precursor in the step (3), the M-type ferrite precursor in the step (3) and a binder, pre-sintering at one time, and sintering at the second time to obtain the Co 2 A Z-type ferrite material;
wherein the substituted metal ion comprises Ba 2+ And/or Sr 2+ 。
The preparation method is simple, the Y-type cation mixed solution and the M-type cation mixed solution are obtained in an ion exchange mode through an electrodialysis method, so that the introduction of impurities is reduced, the purity of metal ions is ensured, and then the M-type ferrite precursor and the Y-type ferrite precursor are preparedThe body is compounded, and Co is obtained by two-step sintering 2 The Z-type ferrite material prepared by the preparation method provided by the invention has the advantages of higher magnetic conductivity, small granularity, uniform mixing and less impurities.
In the invention, the Y-type cation mixed solution and the M-type cation mixed solution prepared by the electrodialysis method have the characteristic of good ion dispersion effect.
Compared with other preparation methods such as a solid phase method and an electrolytic coprecipitation method, the electrodialysis method has the advantages of high material purity, less impurity introduction and good metal ion dispersibility.
According to the invention, the primary presintering is carried out firstly, and then the secondary sintering is carried out, so that the full sintering is facilitated, the phase forming effect is better, the generated Z-type ferrite phase is purer, if only one step is carried out, the impurity phase is relatively more, and the generated Z-type ferrite is difficult.
Preferably, the Fe contained in step (1) 3+ Soluble metal salt of (2), co-containing 2+ The soluble metal salt of (2) and the soluble metal salt containing a substituted metal ion include any one of a chloride salt, a nitrate salt or an organic salt or a combination of at least two thereof.
Preferably, the ion exchange membrane used in the electrodialysis method in step (2) comprises any one of an anion exchange membrane, a cation exchange membrane or an ion exchange composite membrane or a combination of at least two of the anion exchange membrane, the cation exchange membrane and the ion exchange composite membrane.
Preferably, the first mixing and the second mixing in step (3) each independently comprise stirring.
Preferably, the time for the first mixing and the second mixing in step (3) is independently 5 to 12h, such as 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h, etc.
Preferably, the temperature of the first drying and the second drying in step (3) is 100 to 120 ℃ independently, such as 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃ and the like.
Preferably, in step (4), the molar ratio of the Y-type ferrite precursor in step (3) to the M-type ferrite precursor in step (3) is (1 to 1.1): 1, for example, 1:1, 1.01.
In the invention, the molar ratio of the Y-type ferrite precursor in the step (3) to the M-type ferrite precursor in the step (3) is too small, which is not favorable for Z-type ferrite to form a phase, and the performance is poor and too large, which leads to low material performance and low purity of Z-type ferrite.
Preferably, the product after the primary pre-burning in the step (4) is ground.
Preferably, the polishing time is 10 to 60s, for example 10s, 20s, 30s, 40s, 50s, 60s, or the like.
Preferably, the temperature of the primary pre-sintering in the step (4) is 1200-1280 ℃, such as 1200 ℃, 1210 ℃, 1220 ℃, 1230 ℃, 1240 ℃, 1250 ℃, 1260 ℃, 1270 ℃ or 1280 ℃ and the like.
In the invention, the temperature of one pre-burning is too high, which is not beneficial to sintering the Z-type ferrite into phases, the product has more impure phases, and the performance is poor and more impure phases are caused due to too low temperature.
Preferably, the time for the one-time pre-burning in the step (4) is 1 to 6 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours.
Preferably, the temperature of the secondary sintering in step (4) is 1100-1200 deg.C, such as 1100 deg.C, 1120 deg.C, 1130 deg.C, 1140 deg.C, 1150 deg.C, 1160 deg.C, 1170 deg.C, 1180 deg.C, 1190 deg.C or 1200 deg.C.
According to the invention, the sintering temperature is reduced by an electrodialysis method, and in the secondary sintering process, the powder particles grow abnormally and have poor particle dispersion effect due to overhigh temperature, and the phase forming effect is poor due to overlow temperature, so that the powder performance is low.
Preferably, the time for the secondary sintering in the step (4) is 1 to 6 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours.
As a preferable technical scheme, the preparation method comprises the following steps:
(1) Will contain Fe 3+ Soluble metal salt of (2), soluble metal salt containing substituted metal ion containing Co 2+ Mixing the soluble metal salt with a solvent to obtainTo a Y-type mixed solution;
will contain Fe 3+ Mixing the soluble metal salt, the soluble metal salt containing the substituted metal ions and the solvent to obtain an M-type mixed solution;
(2) Treating the Y-type mixed solution in the step (1) and the M-type mixed solution in the step (1) respectively by adopting an electrodialysis method to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) Stirring the Y-type cation mixed solution obtained in the step (2) and ammonium bicarbonate for 5-12 hours, and drying at 100-120 ℃ to obtain a Y-type ferrite precursor;
stirring the M-type cation mixed solution obtained in the step (2) and ammonium bicarbonate for 5-12 h, and drying at 100-120 ℃ to obtain an M-type ferrite precursor;
(4) Carrying out compression molding on the Y-type ferrite precursor in the step (3) and the M-type ferrite precursor in the step (3) according to the molar ratio of (1-1.1) to 1 and a binder, presintering for 1-6 h at 1200-1280 ℃, and grinding the product after the presintering for 10-60 s; then secondary sintering is carried out for 1 to 6 hours at the temperature of 1100 to 1200 ℃, and the Co is obtained 2 A Z-type ferrite material;
wherein the substituted metal ion comprises Ba 2+ And/or Sr 2+ 。
In a second aspect, the present invention provides a Co 2 Preparation method of Z-type ferrite material, co 2 The Z-type ferrite material is made of Co as described in the first aspect 2 The Z-type ferrite material is prepared by the preparation method.
In a third aspect, the invention also provides Co 2 Use of a Z-type ferrite material of Co as described in the second aspect 2 The Z-type ferrite material is used for ultrahigh frequency magnetic devices.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares Co with uniform mixing, smaller granularity and higher magnetic conductivity by an electrodialysis method 2 The Z-type ferrite material is suitable for ultrahigh frequency magnetic devices, reduces the sintering temperature and saves the preparation laborThe ferrite material prepared by the invention has the grain size of less than 0.88 μm, the initial magnetic permeability μ' of more than 3.9 and the dielectric loss tangent tan delta of less than 0.045.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The present embodiment provides a Co 2 Z-type ferrite material, said Co 2 The preparation method of the Z-type ferrite material comprises the following steps:
(1) Weigh 0.052mol of Ba (NO) 3 ) 2 0.1mol of Co (NO) 3 ) 2 0.6mol of Fe (NO) 3 ) 3 Dissolving in 0.5L deionized water, and completely dissolving to obtain Y-shaped mixed solution;
weigh 0.052mol of Ba (NO) 3 ) 2 0.6mol of Fe (NO) 3 ) 3 Dissolving in 0.5L deionized water, and completely dissolving to obtain M-type mixed solution;
(2) Electrodialysis of NO in solution 3- Separating by an anion exchange membrane to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) Respectively adding 1mol of ammonium bicarbonate into the Y-type cation mixed solution and the M-type cation mixed solution obtained in the step (2), stirring for 8h at normal temperature, and then placing in a drying oven at 100 ℃ for drying to obtain a Y-type ferrite precursor and an M-type ferrite precursor;
(4) Sieving the Y-type ferrite precursor in the step (3) and the M-type ferrite precursor in the step (3), respectively weighing 0.03mol according to the molar ratio of 1:1, mixing, adding 0.3wt% of PVA binder for granulation and pressing into blocks, presintering at 1250 ℃ for one time, and preserving heat for 4 hours;
(5) Vibrating and grinding the product after the primary presintering for 20s, sintering at 1150 ℃, and preserving heat for 4h to obtain the Co 2 A Z-type ferrite material.
Example 2
The present embodiment provides a Co 2 Z-type ferrite material, said Co 2 The preparation method of the Z-type ferrite material comprises the following steps:
(1) Weigh 0.052mol of Ba (NO) 3 ) 2 0.1mol of Co (NO) 3 ) 2 0.6mol of Fe (NO) 3 ) 3 Dissolving in 0.5L deionized water, and completely dissolving to obtain Y-shaped mixed solution;
0.052mol of Sr (NO) is weighed 3 ) 2 0.6mol of Fe (NO) 3 ) 3 Dissolving in 0.5L deionized water, and completely dissolving to obtain M-type mixed solution;
(2) Electrodialysis of NO in solution 3- Separating by an anion exchange membrane to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) Respectively adding 1mol of ammonium bicarbonate into the Y-type cation mixed solution and the M-type cation mixed solution obtained in the step (2), stirring for 5h at normal temperature, and then placing in a drying oven at 120 ℃ for drying to obtain a Y-type ferrite precursor and an M-type ferrite precursor;
(4) Sieving the Y-type ferrite precursor in the step (3) and the M-type ferrite precursor in the step (3), mixing according to a molar ratio of 1.05;
(5) Vibrating and grinding the product after the primary presintering for 60s, sintering at 1100 ℃, and preserving heat for 6h to obtain the Co 2 A Z-type ferrite material.
Example 3
The present embodiment provides a Co 2 Z-type ferrite material, said Co 2 The preparation method of the Z-type ferrite material comprises the following steps:
(1) 0.052mol of Sr (NO) is weighed 3 ) 2 0.1mol of Co (NO) 3 ) 2 0.6mol of Fe (NO) 3 ) 3 Dissolving in 0.5L deionized water, and completely dissolving to obtain Y-shaped mixed solution;
0.052mol of Sr (NO) is weighed 3 ) 2 0.6mol of Fe (NO) 3 ) 3 Dissolved in 0.5L of deionized waterFully dissolving to obtain an M-type mixed solution;
(2) Electrodialysis of NO in solution 3- Separating through an anion exchange membrane to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) Respectively adding 1mol of ammonium bicarbonate into the Y-type cation mixed solution and the M-type cation mixed solution obtained in the step (2), stirring for 12h at normal temperature, and then placing in a drying oven at 110 ℃ for drying to obtain a Y-type ferrite precursor and an M-type ferrite precursor;
(4) Sieving the Y-type ferrite precursor in the step (3) and the M-type ferrite precursor in the step (3), mixing according to a molar ratio of 1.1;
(5) Vibrating and grinding the product after the primary presintering for 40s, sintering at 1200 ℃, and preserving heat for 1h to obtain the Co 2 A Z-type ferrite material.
Example 4
The difference between this example and example 1 is that in step (1) of this example, the raw material for the Y-type mixed solution was 0.052mol of SrCl 2 0.1mol of CoCl 2 And 0.6mol FeCl 3 (ii) a The raw material of the M type mixed solution was molSrCl of 0.052 2 And molFeCl of 0.6 3 。
The remaining preparation methods and parameters were in accordance with example 1.
Example 5
The difference between this example and example 1 is that in step (1) of this example, the raw material of the Y-type mixed solution is 0.052mol of BaCl 2 0.1mol of CoCl 2 And 0.6mol of FeCl 3 (ii) a The raw material of the M-type mixed solution was molBaCl of 0.052 2 And molFeCl of 0.6 3 。
The remaining preparation methods and parameters were in accordance with example 1.
Example 6
The difference between this example and example 1 is that the primary calcination temperature in step (4) of this example is 1350 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Example 7
The difference between this example and example 1 is that the primary calcination temperature in step (4) of this example is 1150 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Example 8
The difference between this example and example 1 is that the sintering temperature in step (5) of this example is 1250 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The Z-type ferrite is prepared according to the coprecipitation method in the comparative example, and the specific implementation mode is as follows:
(1) 0.15mol of Ba (NO) was weighed 3 ) 2 0.1mol of Co (NO) 3 ) 2 1.2mol of Fe (NO) 3 ) 3 Dissolving in 0.5L deionized water to obtain a mixed solution;
(2) Adding 2mol of sodium carbonate into the mixed solution obtained in the step (1), stirring for 8h at normal temperature, and standing;
(3) And (3) centrifuging the mixture obtained in the step (2), filtering and drying to obtain a precipitate.
(4) Adding 0.3wt% of PVA binder, granulating, pressing into blocks, presintering at 1250 ℃ for one time, and preserving heat for 4 hours;
(5) Vibrating and grinding the product after the primary presintering for 20s, sintering at 1150 ℃, and preserving heat for 4h to obtain the Co 2 A Z-type ferrite material.
Comparative example 2
The comparative example prepares the Z-type ferrite according to a solid phase method, and the specific implementation mode is as follows:
(1) 0.15mol of BaCO3,0.1mol of CoO,0.6mol of Fe were weighed out 2 O 3 Ball milling and mixing for 2h;
(2) Drying and presintering at 1250 ℃ for 2h;
(3) Performing secondary ball milling for 2 hours, and drying;
(4) And (4) after drying, carrying out vibromilling for 20s, sintering at 1150 ℃ and preserving heat for 4h to obtain the Z-type ferrite.
Comparative example 3
The comparative example is different from example 1 in that the secondary sintering was directly performed without primary calcination.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 4
The comparative example is different from example 1 in that only one firing is performed and secondary sintering is not performed.
The remaining preparation methods and parameters were in accordance with example 1.
Co prepared in examples 1 to 8 and comparative examples 1 to 4 2 A Z-type ferrite material was mixed with a 6wt% PVA solution, pressed into an annular blank, and then calcined at 1280 ℃ to prepare a sample, and the initial permeability μ' and loss tangent tan δ of the sample were measured.
Co obtained in examples 1 to 2 and comparative examples 1 to 4 was measured by a scanning electron microscope and a laser particle size analyzer 2 Particle size of the Z-type ferrite material. The results of measurement of the particle size, initial permeability μ', and dielectric loss tangent tan δ are shown in Table 1.
TABLE 1
From the data results of example 1 and examples 6 and 7, it is known that the temperature of one-time pre-sintering is too high, which is not favorable for subsequent crushing, the particles are large, the loss is too high, and the temperature is too low, which causes phase difference and lowers the powder magnetic permeability.
From the data results of examples 1 and 8, it is understood that the particle size is increased and the loss is increased due to the excessively high temperature of the secondary sintering.
As can be seen from the data results of examples 1-8 and comparative examples 1-2, co prepared by the preparation method provided by the present invention 2 The Z-type ferrite material has relatively small granularity and small dielectric loss tangent.
As can be seen from the data results of example 1 and comparative examples 3 and 4, the Z-type ferrite having high purity cannot be efficiently prepared by only one calcination or only two sinterings.
In conclusion, the invention prepares Co with uniform mixing, smaller granularity and higher magnetic permeability by an electrodialysis method 2 The ferrite material of Z type, suitable for in the ultra-high frequency magnetic device, and reduced the sintering temperature, has saved the preparation process, the ferrite material prepared by the invention, its granulometry is under 0.88 μm, and the initial permeability μ' is above 3.9, the dielectric loss tangent tan delta is under 0.045.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (16)
1. Co 2 The preparation method of the Z-type ferrite material is characterized by comprising the following steps of:
(1) Will contain Fe 3+ Soluble metal salt of (2), soluble metal salt containing substituted metal ion, soluble metal salt containing Co 2+ Mixing the soluble metal salt with a solvent to obtain a Y-shaped mixed solution;
will contain Fe 3+ Mixing the soluble metal salt, the soluble metal salt containing the substituted metal ions and the solvent to obtain an M-type mixed solution;
(2) Treating the Y-type mixed solution in the step (1) and the M-type mixed solution in the step (1) respectively by adopting an electrodialysis method to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) Carrying out first mixing on the Y-type cation mixed solution obtained in the step (2) and ammonium bicarbonate, and carrying out first drying to obtain a Y-type ferrite precursor;
carrying out second mixing on the M-type cation mixed solution obtained in the step (2) and ammonium bicarbonate, and carrying out second drying to obtain an M-type ferrite precursor;
(4) The Y type in the step (3)Performing compression molding on the ferrite precursor, the M-type ferrite precursor in the step (3) and a binder, pre-sintering at one time, and sintering at a second time to obtain the Co 2 A Z-type ferrite material;
wherein the substituted metal ion comprises Ba 2+ And/or Sr 2+ 。
2. Co of claim 1 2 The preparation method of the Z-type ferrite material is characterized in that the Fe contained in the step (1) 3+ Soluble metal salt of (2), co-containing 2+ The soluble metal salt of (2) and the soluble metal salt containing a substituted metal ion include any one of a chloride salt, a nitrate salt, or an organic salt or a combination of at least two thereof.
3. Co according to claim 1 2 The preparation method of the Z-type ferrite material is characterized in that the ion exchange membrane used in the electrodialysis method in the step (2) comprises any one of an anion exchange membrane, a cation exchange membrane or an ion exchange composite membrane or the combination of at least two of the anion exchange membrane, the cation exchange membrane and the ion exchange composite membrane.
4. Co according to claim 1 2 A method for preparing a Z-type ferrite material, wherein the first mixing and the second mixing in step (3) each independently comprise stirring.
5. Co of claim 1 2 The preparation method of the Z-type ferrite material is characterized in that the time of the first mixing and the second mixing in the step (3) is 5 to 12 hours respectively and independently.
6. Co according to claim 1 2 The preparation method of the Z-type ferrite material is characterized in that the temperatures of the first drying and the second drying in the step (3) are respectively and independently 100-120 ℃.
7. Co according to claim 1 2 A preparation method of Z-type ferrite material is characterized in that,in the step (4), the molar ratio of the Y-type ferrite precursor in the step (3) to the M-type ferrite precursor in the step (3) is (1-1.1): 1.
8. Co according to claim 1 2 The preparation method of the Z-type ferrite material is characterized in that the product obtained after the primary presintering in the step (4) is ground.
9. Co according to claim 8 2 The preparation method of the Z-type ferrite material is characterized in that the grinding time is 10-60 s.
10. Co according to claim 1 2 The preparation method of the Z-type ferrite material is characterized in that the temperature of the one-time presintering in the step (4) is 1200-1280 ℃.
11. Co according to claim 1 2 The preparation method of the Z-type ferrite material is characterized in that the time of the primary pre-sintering in the step (4) is 1-6 h.
12. Co according to claim 1 2 The preparation method of the Z-type ferrite material is characterized in that the temperature of the secondary sintering in the step (4) is 1100-1200 ℃.
13. The method for preparing a Co 2Z-type ferrite material according to claim 1, wherein the time of the secondary sintering in the step (4) is 1 to 6 hours.
14. Co according to claim 1 2 The preparation method of the Z-type ferrite material is characterized by comprising the following steps of:
(1) Will contain Fe 3+ Soluble metal salt of (2), soluble metal salt containing substituted metal ion containing Co 2+ Mixing the soluble metal salt with a solvent to obtain a Y-shaped mixed solution;
will contain Fe 3+ Soluble metal salt of (2), substituted metal-containingMixing soluble metal salt of ions with a solvent to obtain an M-type mixed solution;
(2) Treating the Y-type mixed solution in the step (1) and the M-type mixed solution in the step (1) respectively by adopting an electrodialysis method to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) Stirring the Y-type cation mixed solution obtained in the step (2) and ammonium bicarbonate for 5-12 h, and drying at 100-120 ℃ to obtain a Y-type ferrite precursor;
stirring the M-type cation mixed solution obtained in the step (2) and ammonium bicarbonate for 5-12 hours, and drying at 100-120 ℃ to obtain an M-type ferrite precursor;
(4) Carrying out compression molding on the Y-type ferrite precursor in the step (3) and the M-type ferrite precursor in the step (3) according to the molar ratio of (1-1.1) to 1 and a binder, presintering for 1-6 h at 1200-1280 ℃, and grinding the product after the presintering for 10-60 s; then secondary sintering is carried out for 1 to 6 hours at the temperature of 1100 to 1200 ℃, and the Co is obtained 2 A Z-type ferrite material;
wherein the substituted metal ion comprises Ba 2+ And/or Sr 2+ 。
15. Co 2 Z-type ferrite material, characterized in that said Co 2 The Z-type ferrite material is made of Co as claimed in any one of claims 1 to 14 2 The Z-type ferrite material is prepared by the preparation method.
16. Co 2 Use of a Z-type ferrite material, characterized in that Co as claimed in claim 15 is used 2 The Z-type ferrite material is used for ultrahigh frequency magnetic devices.
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