CN116789448B - Medium-temperature sintering high-Q-value microwave dielectric material and preparation method and application thereof - Google Patents
Medium-temperature sintering high-Q-value microwave dielectric material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a medium-temperature sintering high-Q-value microwave dielectric material and a preparation method thereof. The chemical composition of the medium-temperature sintering high-Q-value microwave dielectric material comprises: a main MgNb 2O6 phase, a low-melting-point Mg-V second phase and a Sb 2O5 phase, wherein the Sb 2O5 phase exists in the ceramic in a solid solution form; the medium-temperature sintering high-Q-value microwave dielectric material contains Mg element: nb element: (V element + Sb element) =1:2-2 x: x is more than or equal to 0.010 and less than or equal to 0.075; the total amount of the V element and the Sb element is x.
Description
Technical Field
The invention relates to a microwave dielectric material with a medium-temperature sintering high Q value and a preparation method thereof, belonging to the field of ceramic materials.
Background
The microwave dielectric ceramic is a functional ceramic applied to a microwave frequency band (300 MHz-300 GHz) as a core device of a dielectric filter, and with the continuous development of the communication industry, a ceramic filter represented by TiO 2 gradually replaces a filter system mainly comprising a metal cavity. In recent years, the rapid development of the fifth generation mobile communication, the demand of microwave dielectric ceramics reaches millions.
The three main directions of the development of microwave dielectric ceramics in recent years are that the dielectric constants are serialized, the temperature coefficient of the resonant frequency is near 0 and the low-temperature co-firing is performed. The dielectric constants are serialized to be suitable for devices with different signal frequency bands, and the device requirements of different sizes are met by adjusting the dielectric constants; the temperature coefficient of the resonant frequency is near 0, which is an important guarantee of the working stability of the device, and the good temperature coefficient of the resonant frequency is a big precondition for realizing the application; the traditional microwave dielectric ceramic is usually sintered at a high temperature above 1200 ℃ to obtain excellent dielectric properties, however, the high-temperature electrode material is high in price on one hand, and on the other hand, is limited to a certain extent in terms of conductivity and other properties, and in order to expand the application range of the microwave dielectric ceramic, a certain amount of sintering auxiliary agent is added to reduce the sintering temperature of the ceramic to 1083 ℃ so that the ceramic can be co-sintered with metallic copper or reduced to 950 ℃ so that the LTCC process can be realized, and the process can be suitable for the preparation of various electronic components, and greatly expands the application range of the microwave dielectric ceramic.
In order to further meet the use requirement of 5G communication on microwave dielectric ceramics, the sintering temperature is reduced, and meanwhile, the material itself is guaranteed to have a higher Qf value so as to guarantee the use requirement of high-frequency and large-flux of microwave communication equipment. Among the existing K20 ceramic systems, mgNb 2O6 ceramic, which is a typical representation of the K20 ceramic system, has a higher Qf value (qf=100,000 ghz), while having a lower cost relative to the tantalate system, and a higher stability relative to the niobate system, which makes it one of the key candidate materials for the new generation of communication technology. Currently, methods for preparing MgNb 2O6 ceramics include various methods such as a solid-phase reaction method, a sol-gel method, and a hydrothermal method. However, the sintering temperature of the system material reaches 1300 ℃, meanwhile, the reduction of the sintering temperature is difficult to realize by taking Mg as a high-temperature metal, and the application range of the system material is limited by the excessively high sintering temperature.
Disclosure of Invention
Aiming at the problems, the invention provides a medium-temperature sintering high-Q-value microwave dielectric material and a preparation method thereof.
In one aspect, the invention provides a medium temperature sintered high Q microwave dielectric material, the chemical composition of which mainly comprises: a main MgNb 2O6 phase, a low-melting-point Mg-V second phase and a Sb 2O5 phase, wherein the Sb 2O5 phase exists in the ceramic in a solid solution form; the medium-temperature sintering high-Q-value microwave dielectric material contains Mg element: nb element: (V element+sb element) =1 (2-2 x): x is more than or equal to 0.010 and less than or equal to 0.075; the total amount of the V element and the Sb element is x.
According to the invention, on the basis of a solid phase reaction method, through the micro substitution (Mg (Nb 1-xGx/2)2O6-2.5x, G=V and Sb)) of V ions and Sb ions on Nb ions in the raw material weighing process, part of low-loss low-melting-point Mg-V second phase is generated, so that the MgNb 2O6 ceramic realizes high compactness and high Qf value while the sintering temperature is reduced.
Preferably, the Mg-V low melting second phase comprises at least one of Mg 3(VO4)2 and Mg 2V2O7.
Preferably, the molar ratio of the V element to the Sb element is 1:0 to 0:1, preferably 9:1 to 7:3, and more preferably 8:2.
Preferably, the dielectric constant of the medium-temperature sintering high-Q-value microwave dielectric material is 19.48-20.30, the dielectric loss is 1.28X10 -4～9.35×10-5, and the Qf value is 78400-107000.
Preferably, the density of the medium-temperature sintering high-Q-value microwave dielectric material is 4.70-4.85 g/cm 3, and the relative density is 95.75-98.00%.
On the other hand, the invention provides a preparation method of the medium-temperature sintered high-Q-value microwave dielectric material, which comprises the following steps:
(1) Weighing and mixing a Mg source, a Nb source, a V source and a Sb source according to Mg (Nb 1-xGx/2)2O6-2.5x, G=V or/and Sb), and presintering at 800-900 ℃ for at least 4 hours to obtain synthetic powder;
(2) Ball milling, granulating and forming the obtained synthetic powder to obtain a ceramic blank;
(3) And after the ceramic blank is subjected to glue discharging, heating to 950-1200 ℃ for heat preservation for 4-6 hours, and cooling to 700-800 ℃ for heat preservation for 4-6 hours to obtain the medium-temperature sintering high-Q-value microwave dielectric material.
According to the invention, the non-stoichiometric ratio of the MgNb 2O6 ceramic matrix (the microwave dielectric material containing Mg, nb and O elements) is used for replacing a small amount of G 2O5 component to play a role in reducing the activation energy of sintering reaction on the ceramic, so that the sintering temperature of the ceramic matrix is successfully reduced, and the medium-temperature sintering is realized. The invention adopts stoichiometric ratio to synthesize Mg (Nb 1-xGx/2)2O6-2.5x powder in the synthesis process, ensures that the G composition can successfully synthesize a low-melting-point second phase on the basis of ensuring the excessive Mg content, thereby realizing the reduction of sintering temperature on the basis of ensuring the microwave dielectric property of the material, and replaces substances (preferably, V 2O5 or V 2O5 and Sb 2O5) composed of at least one of two oxides of V 2O5 and Sb 2O5, wherein the two oxides have lower melting points, can generate a low-loss low-melting-point second phase with excessive Mg in the reaction process, is beneficial to reducing the sintering temperature of a ceramic matrix on the basis of ensuring the excessive Mg content, widens the application of MgNb 2O6 ceramics in the field of medium-temperature cofiring, and expands the application market.
Preferably, in the step (1), the Mg source is MgO powder or/and basic MgCO 3 powder; the Nb source is Nb 2O5 powder; the V source is V 2O5 powder; the Sb source is Sb 2O5 powder; preferably, the particle size D 90 of the V source and the Sb source is less than 3 μm.
Preferably, in the step (1), the molar ratio of the V source to the Sb source is 0:1 to 1:0, preferably 9:1 to 7:3, more preferably 8:2.
Preferably, in the step (2), a binder is added during granulation, and the binder is a polyvinyl alcohol aqueous solution; the concentration of the polyvinyl alcohol aqueous solution is 4-8wt%.
Preferably, in the step (3), the temperature of the adhesive discharging is 400-600 ℃ and the time is 1-2 hours; the heating rate is 4-10 ℃/min; the cooling rate is 1-5 ℃/min.
In the invention, the medium-temperature sintering high-Q microwave dielectric material can be used for preparing an LTCC substrate, particularly for preparing the LTCC substrate by co-firing with Cu metal in a reducing atmosphere, and the sintering is realized at 950-1200 ℃.
The beneficial effects are that:
The dielectric constant of the microwave dielectric ceramic material prepared by the invention is 19.52, the resonance temperature coefficient is-70 ppm/DEG C, the higher Qf value 101300GHz and the sintering system is 1050 ℃/4h, and the microwave dielectric ceramic material can be used as a key core material of electronic components such as an antenna, a substrate and the like for microwave mobile communication and is widely applied to the fifth generation mobile communication industry. Compared with the prior art, the method for preparing MgNb 2O6 ceramic which can be used for medium-temperature sintering has the characteristics of simple process, can obviously improve the yield of the material while ensuring the material performance, is suitable for large-scale industrial production, and has important application value.
Drawings
FIG. 1 shows XRD patterns of the microwave dielectric materials before and after doping the G component prepared in example 1, example 2, example 3 and example 4;
FIG. 2 is an enlarged XRD pattern of the microwave dielectric materials before and after doping the G component prepared in example 1, example 2, example 3 and example 4;
Fig. 3 shows the dielectric constant values of the microwave dielectric materials before and after doping the G component prepared in example 1, example 2, example 3, and example 4;
fig. 4 shows Qf values of the microwave dielectric materials before and after doping the G component prepared in example 1, example 2, example 3, and example 4.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the present disclosure, the medium temperature sintered high Q microwave dielectric material is composed of Mg (Nb 1-xGx/2)2O6-2.5x system, the main body of which is a microwave dielectric material containing Mg, nb and O elements, and the G component contains two elements of V or/and Sb, wherein Qf is preferably not lower than 78400.
Preferably, the ratio of V to Sb is 0.9:0.1 to 0.7:0.3, preferably 0.8:0.2. Wherein x is from 0.01 to 0.075, more preferably from 0.025 to 0.05. Too high substitution amount of G is easy to cause deterioration of material performance, and a small amount of G can be added to effectively reduce sintering temperature of the material on the basis of keeping high Qf value.
The following exemplarily illustrates a preparation method of the medium-temperature sintered high-Q-value microwave dielectric material.
And (3) preparing synthetic powder. The method comprises the steps of mixing Mg source, nb source and G source (V source and Sb source) according to the composition of Mg (Nb 1-xGx/2)2O6-2.5x), and then presintering and synthesizing to obtain synthetic powder, wherein the molar substitution amount of G is between 0.05 and 0.20, the Mg source can be MgO or basic MgCO 3, the Nb source can be Nb 2O5, the V source can be V 2O5, the Sb source can be Sb 2O5, as an example, the raw materials of the microwave dielectric material are weighed according to the molar ratio of Mg (Nb 1-xGx/2)2O6-2.5x, then water is added, zirconium balls are ground into slurry on a planetary ball mill, and then the slurry is dried and calcined and synthesized to obtain the synthetic powder, wherein the ball milling slurry granularity D 50 is less than 3 mu m, the presintering and synthesizing temperature is 800-900 ℃, the heat preservation time is not less than 4 hours, and the preferential presintering temperature is 850 ℃.
Wherein the G source may be G 2O5, such as V 2O5 and Sb 2O5, etc. Preferably, the molar ratio of the two V 2O5 and Sb 2O5 is controlled to be 9:1 to 7:3, preferably 8:2.
And ball milling, granulating and forming the synthesized powder to obtain a ceramic blank.
And sintering the ceramic blank under a specific sintering system to obtain the microwave dielectric material with the ultrahigh Q value. The specific sintering schedule includes: heating to 950-1150 ℃ at 5-10 ℃/min, preserving heat for 4-6 hours, then cooling to 700-800 ℃ at 1 ℃/min, and preserving heat for 4-6 hours.
In the invention, a vector network analyzer is adopted to test the dielectric constant of the obtained medium-temperature sintering high-Q-value microwave dielectric material. And testing the dielectric loss of the obtained medium-temperature sintered high-Q-value microwave dielectric material by adopting a vector network analyzer. And testing the density of the medium-temperature sintered high-Q-value microwave dielectric material by adopting an Archimedes drainage method. And testing the relative density of the medium-temperature sintered high-Q-value microwave dielectric material by adopting an Archimedes drainage method. And testing the Qf of the obtained medium-temperature sintered high-Q-value microwave dielectric material by adopting a vector network analyzer.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
(1) Accurately weighing Nb 2O5 0.975 moL, basic MgCO 3 1.0.0 moL and G 2O5 0.0125.0125 moL (x=0.025, G is two elements of V and Sb, the ratio of the two elements is 0.8:0.2), adding into a nylon ball milling tank, pouring into zirconia balls with the diameter of 10mm in deionized water, wherein the weight ratio is as follows: ball: water = 1:2:1.5; ball milling time is 4 hours, the granularity D50 of ball milling slurry is 3, and after ball milling, the slurry is dried and dried in an oven at 120 ℃ for one night. Placing the dried powder into a sagger, calcining for 4 hours at 850 ℃, and cooling along with a furnace to obtain synthetic powder;
(2) 100g of the synthetic powder was weighed, added to a nylon ball mill tank, and deionized water and zirconia balls with a diameter of 10mm were poured. The weight ratio of the materials is as follows: ball: water = 1:2:1.5; the ball milling time was 4 hours until the ball milling slurry particle size D 50 was 3 μm. After ball milling, the slurry is poured into a enamel tray, put into an oven and dried at 130 ℃. Granulating with PVA water solution to obtain granulated powder. Placing the granulated powder into a die with the diameter of 6mm for molding under the pressure of 100MPa, and setting the height of a molded sample to be 4mm to obtain a ceramic blank;
(3) And (3) placing the ceramic blank into a muffle furnace, heating to 600 ℃ at a speed of 4 ℃/min, preserving heat for 2 hours, and performing glue discharging treatment. Then heating to 1150 ℃ at the speed of 4 ℃/min, preserving heat for 4 hours, then cooling to 800 ℃ at the speed of 1 ℃/min, and preserving heat for 5 hours to obtain the microwave dielectric material, wherein the performance is shown in table 1.
Example 2
The preparation process of the microwave dielectric material in this embodiment 2 is described with reference to embodiment 1, and the difference is that: x=0.050; then the five samples are respectively heated to 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ and heat-preserving for 4 hours according to the speed of 4 ℃/min, then 1 ℃/min is reduced to 800 ℃ and heat-preserving for 5 hours, and the microwave medium material is prepared.
Example 3
The preparation process of the microwave dielectric material in this embodiment 3 is described with reference to embodiment 2, and the difference is that: x=0.075.
Example 4
The preparation process of the microwave dielectric material in this example 4 is described with reference to example 2, except that: x=0.010.
Example 5
The preparation process of the microwave dielectric material in this example 5 is described with reference to example 2, except that: x=0.040.
Example 6
The preparation process of the microwave dielectric material in this example 6 is described with reference to example 2, except that: x=0.060.
Example 7
The preparation process of the microwave dielectric material in this example 7 is described with reference to example 2, except that: v: sb=9:1.
Example 8
The preparation process of the microwave dielectric material in this example 8 is described with reference to example 2, except that: v: sb=7:3, its samples were raised to 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃ respectively.
Example 9
The preparation process of the microwave dielectric material in this example 9 is described with reference to example 2, except that: v: sb=6:1, the samples of which were raised to 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ and 1200 ℃ respectively.
Example 10
The preparation process of the microwave dielectric material in this embodiment 10 is described with reference to embodiment 2, except that: v: sb=5:5, and the samples were heated to 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ and 1200 ℃ respectively.
Example 11
The preparation process of the microwave dielectric material in this example 11 is described with reference to example 2, except that: v: sb=1:0.
Example 12
The preparation process of the microwave dielectric material in this embodiment 12 is described with reference to embodiment 2, except that: v: sb=0:1, and the samples thereof were heated to 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, respectively.
Comparative example 1
The procedure for the preparation of the microwave dielectric material of this comparative example 1 is described with reference to example 2, with the difference that: the preparation of the synthetic powder comprises the following steps: 1.0moL of MgNb 2O6 powder, 0.025moL of V 2O5 powder and Sb 2O5 powder (V: sb=8:2) were mixed as a synthetic powder.
Comparative example 2
The procedure for preparing the microwave dielectric material in this comparative example 2 is described with reference to example 2, except that: the raw materials were weighed according to the Mg (Nb 1-xGx)2O6) deficiency.
Table 1 shows the composition and properties of the microwave dielectric material prepared by the invention
Fig. 1 and 2 show XRD patterns of the microwave dielectric materials before and after doping the G component prepared in example 1, example 2, example 3, and example 4, and it can be seen that the main crystal phase is MgNb 2O6 and a small amount of Mg-V low melting point second phase is obtained after substituting the sintering aid of the present invention. Fig. 3 and 4 are graphs showing the effect of the substitution of the sintering aid oxide of the present invention on the dielectric constant and the quality factor of the ceramic according to example 1, wherein the substitution amount of G is 0.010, 0.025, 0.050, and 0.075, respectively, corresponding to examples 1, 2,3, and 4 of the present invention, it can be seen that the sintering temperature of the ceramic can be reduced while maintaining a high quality factor, but the sintering temperature of the material is not significantly reduced when the substitution amount is too high, and the quality factor is reduced.
Claims (9)
1. The medium-temperature sintering high-Q-value microwave dielectric material is characterized by comprising the following chemical components in percentage by weight: a main MgNb 2O6 phase, a low-melting-point Mg-V second phase and a Sb 2O5 phase, wherein the Sb 2O5 phase exists in the ceramic in a solid solution form; the Mg-V low melting second phase comprises at least one of Mg 3(VO4)2 and Mg 2V2O7; the medium-temperature sintering high-Q-value microwave dielectric material contains Mg element: nb element: (V element + Sb element) =1:2-2 x: x is more than or equal to 0.010 and less than or equal to 0.075; the total amount of the V element and the Sb element is x; the molar ratio of the V element to the Sb element is 9:1-7:3;
the preparation method of the medium-temperature sintering high-Q-value microwave dielectric material comprises the following steps:
(1) Weighing and mixing a Mg source, a Nb source, a V source and a Sb source according to Mg (Nb 1-xGx/2)2O6-2.5x, G=V and Sb), and presintering at 800-900 ℃ for at least 4 hours to obtain synthetic powder, wherein the molar ratio of the V source to the Sb source is 9:1-7:3;
(2) Ball milling, granulating and forming the obtained synthetic powder to obtain a ceramic blank;
(3) And after the ceramic blank is subjected to glue discharging, heating to 1000-1200 ℃ for heat preservation for 4-6 hours, and cooling to 700-800 ℃ for heat preservation for 4-6 hours to obtain the medium-temperature sintering high-Q-value microwave dielectric material.
2. The medium temperature sintered high Q microwave dielectric material of claim 1, wherein the molar ratio of V element to Sb element is 8:2.
3. The medium temperature sintered high Q microwave dielectric material according to claim 1, characterized in that the medium temperature sintered high Q microwave dielectric material has a dielectric constant of 19.48-20.30, a dielectric loss of 1.28 x 10 -4～9.35×10-5, and a Qf value of 78400-107000.
4. The medium temperature sintered high Q microwave dielectric material according to any one of claims 1-3, wherein the medium temperature sintered high Q microwave dielectric material has a density of 4.70-4.85 g/cm 3 and a relative density of 95.75-98.00%.
5. The medium temperature sintered high Q value microwave dielectric material according to claim 1, wherein in the step (1), the Mg source is MgO powder or/and basic MgCO 3 powder; the Nb source is Nb 2O5 powder; the V source is V 2O5 powder; the Sb source is Sb 2O5 powder.
6. The medium temperature sintered high Q microwave dielectric material according to claim 5, where in step (1), the V source and Sb source have a particle size D 90 < 3 μm.
7. The medium temperature sintered high Q microwave dielectric material according to any one of claims 1 to 6, wherein in step (2), a binder is added during granulation, and the binder is an aqueous solution of polyvinyl alcohol; the concentration of the polyvinyl alcohol aqueous solution is 4-8wt%.
8. The medium temperature sintered high Q microwave dielectric material according to any one of claims 1 to 6, wherein in step (3), the temperature of the paste ejection is 400 to 600 ℃ for 1 to 2 hours; the heating rate is 4-10 ℃/min; the cooling rate is 1-5 ℃/min.
9. Use of a medium temperature sintered high Q microwave dielectric material according to any one of claims 1-8 in the preparation of an LTCC substrate.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1072258A (en) * | 1996-06-28 | 1998-03-17 | Rii Hyoojongu | Dielectric ceramic composition |
| KR19990008479A (en) * | 1996-06-11 | 1999-02-05 | 이효종 | Ceramic Dielectric Compositions for High Frequency |
| JP2004107195A (en) * | 2002-07-22 | 2004-04-08 | Japan Fine Ceramics Center | Microwave dielectric porcelain composition and microwave dielectric porcelain composition for substrate |
| JP2005272249A (en) * | 2004-03-25 | 2005-10-06 | Tdk Corp | Dielectric ceramic composition, method for producing the same, and dielectric resonator |
| CN1724464A (en) * | 2005-06-24 | 2006-01-25 | 陕西师范大学 | Magnesium columbate microweve medium ceramic and its preparation process |
| KR20110066906A (en) * | 2011-05-18 | 2011-06-17 | 한국과학기술연구원 | Microwave dielectric ceramic compositions for low temperature sintering |
| CN107382313A (en) * | 2017-06-02 | 2017-11-24 | 中国科学院上海硅酸盐研究所 | A kind of microwave-medium ceramics of ultra high quality factor, middle low-k and nearly zero-temperature coefficient and preparation method thereof |
| CN109354495A (en) * | 2018-09-30 | 2019-02-19 | 天津大学 | Magnesium zirconium niobium antimony series microwave dielectric ceramic and preparation method and application |
| CN110407579A (en) * | 2018-04-28 | 2019-11-05 | 中国科学院上海硅酸盐研究所 | One kind having ultrahigh Q-value microwave dielectric material and preparation method thereof |
| JP2021082537A (en) * | 2019-11-21 | 2021-05-27 | パナソニックＩｐマネジメント株式会社 | Magnesium ion secondary battery, positive electrode active material for magnesium ion secondary battery and positive electrode for magnesium ion secondary battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848132A (en) * | 2020-07-30 | 2020-10-30 | 电子科技大学 | Easy-to-sinter high Q value Li3Mg2SbO6Microwave-based dielectric ceramic material and preparation method thereof |
-
2022
- 2022-03-14 CN CN202210248023.9A patent/CN116789448B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990008479A (en) * | 1996-06-11 | 1999-02-05 | 이효종 | Ceramic Dielectric Compositions for High Frequency |
| JPH1072258A (en) * | 1996-06-28 | 1998-03-17 | Rii Hyoojongu | Dielectric ceramic composition |
| JP2004107195A (en) * | 2002-07-22 | 2004-04-08 | Japan Fine Ceramics Center | Microwave dielectric porcelain composition and microwave dielectric porcelain composition for substrate |
| JP2005272249A (en) * | 2004-03-25 | 2005-10-06 | Tdk Corp | Dielectric ceramic composition, method for producing the same, and dielectric resonator |
| CN1724464A (en) * | 2005-06-24 | 2006-01-25 | 陕西师范大学 | Magnesium columbate microweve medium ceramic and its preparation process |
| KR20110066906A (en) * | 2011-05-18 | 2011-06-17 | 한국과학기술연구원 | Microwave dielectric ceramic compositions for low temperature sintering |
| CN107382313A (en) * | 2017-06-02 | 2017-11-24 | 中国科学院上海硅酸盐研究所 | A kind of microwave-medium ceramics of ultra high quality factor, middle low-k and nearly zero-temperature coefficient and preparation method thereof |
| CN110407579A (en) * | 2018-04-28 | 2019-11-05 | 中国科学院上海硅酸盐研究所 | One kind having ultrahigh Q-value microwave dielectric material and preparation method thereof |
| CN109354495A (en) * | 2018-09-30 | 2019-02-19 | 天津大学 | Magnesium zirconium niobium antimony series microwave dielectric ceramic and preparation method and application |
| JP2021082537A (en) * | 2019-11-21 | 2021-05-27 | パナソニックＩｐマネジメント株式会社 | Magnesium ion secondary battery, positive electrode active material for magnesium ion secondary battery and positive electrode for magnesium ion secondary battery |
Non-Patent Citations (4)
| Title |
|---|
| 掺杂V_2O_5对MgNb_2O_6介电陶瓷工艺和性能的影响;赵永乐;赵能伟;刘林艳;;佛山陶瓷;20071215(12);第16-19页 * |
| 掺杂V2O5对MgNb2O6介电陶瓷工艺和性能的影响;赵永乐等人;《佛山陶瓷》;20071215;第12卷;12-15 * |
| 高能球磨时间对MgNb_2O_6陶瓷显微结构和微波介电性能的影响;付志粉;马建立;刘鹏;汤永新;高娟;;硅酸盐通报;20121215(06);第77-80页 * |
| 高能球磨法制备MgNb_2O_6粉体及其陶瓷性能;付志粉;马建立;高娟;刘鹏;;科技导报;20130708(19);第64-67页 * |
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