CN111517787A - Silver niobate-based antiferroelectric ceramic material and preparation method and application thereof - Google Patents
Silver niobate-based antiferroelectric ceramic material and preparation method and application thereof Download PDFInfo
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 126
- 239000004332 silver Substances 0.000 title claims abstract description 126
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 117
- 239000000919 ceramic Substances 0.000 claims abstract description 56
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 42
- 238000004146 energy storage Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000008187 granular material Substances 0.000 claims abstract description 28
- 238000005245 sintering Methods 0.000 claims abstract description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910017677 NH4H2 Inorganic materials 0.000 claims abstract description 19
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229920003023 plastic Polymers 0.000 claims abstract description 10
- 239000004033 plastic Substances 0.000 claims abstract description 10
- 239000003985 ceramic capacitor Substances 0.000 claims abstract description 9
- 238000005498 polishing Methods 0.000 claims abstract description 7
- 238000007639 printing Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 84
- 239000011230 binding agent Substances 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 25
- 238000003825 pressing Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000007873 sieving Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 101710134784 Agnoprotein Proteins 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 91
- 239000011734 sodium Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 15
- 230000008859 change Effects 0.000 description 12
- 230000010287 polarization Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000005684 electric field Effects 0.000 description 9
- 238000010532 solid phase synthesis reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 238000010304 firing Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910017665 NH4HF2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
The invention relates to a silver niobate-based antiferroelectric ceramic material and a preparation method and application thereof, wherein the chemical formula of the silver niobate-based antiferroelectric ceramic material is Ag1‑xNaxNbO3，0<x is less than or equal to 0.5; the preparation method comprises the following steps: first of all by AgNO3Preparation of Ag2O, then with Ag2O、NaOH、Nb2O5And NH4H2F is used as a raw material to carry out hydrothermal reaction, then the product of the hydrothermal reaction is prepared into granules, the granules are prepared into a ceramic blank, and finally the ceramic blank is subjected to plastic removal under a certain temperature condition and then is subjected to one stepSintering the mixture into a ceramic under a constant temperature condition to obtain the silver niobate-based antiferroelectric ceramic material; the application is as follows: and polishing the surface of the silver niobate-based antiferroelectric ceramic material, printing silver paste, and burning silver at the temperature of 500-700 ℃ to obtain the silver niobate-based antiferroelectric ceramic capacitor. The preparation method is simple, oxygen does not need to be introduced into the sintering process, and the prepared product has higher effective energy storage density.
Description
Technical Field
The invention belongs to the technical field of functional ceramic materials, and relates to a silver niobate-based antiferroelectric ceramic material and a preparation method thereof.
Background
The ceramic dielectric capacitor has the advantages of rapid charge and discharge, high power density, cyclic aging resistance, high temperature resistance, high voltage resistance and the like, and has wide application in the fields of pulse power supplies, high-power electronic devices and the like. The current research direction is to further increase the energy storage density to expand the applications.
The dielectric material used in the ceramic dielectric capacitor is linear dielectric ceramic, ferroelectric ceramic, antiferroelectric ceramic and the like, wherein the antiferroelectric ceramic material has a double hysteresis loop, and can realize high energy storage density by utilizing the sudden increase of polarization intensity under a phase change electric field, the main antiferroelectric ceramic is PZT with high zirconium content, but the lead-free antiferroelectric energy storage ceramic material is very important to develop because the lead-free antiferroelectric energy storage ceramic material can bring harm to health and ecological environment.
In recent years, AgNbO has been found3The ceramics have good energy storage characteristics, and antiferroelectric AgNbO is reported in document 1(Tian Ye et. journal of Materials Chemistry A,2016,4(44),17279-3Energy storage studies. Wherein, AgNbO3The preparation is all synthesized by a solid phase method, and the raw material Ag is used2O is easily decomposed in air because oxygen is required to block Ag during the preparation process2The decomposition of O, the preparation period is long, the energy consumption is huge, and the synthetic product is not easy to control.
In the prior art, silver oxide is easy to decompose without oxygen, so that a large amount of impurity phases are generated in solid phase synthesis, pure perovskite structure silver niobate ceramics cannot be synthesized, and performance is further deteriorated.
In addition, the silver niobate in the prior art has higher remanent polarization and lower phase-change electric field intensity, so that the effective energy storage density is not high.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a silver niobate-based antiferroelectric ceramic material and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a silver niobate-based antiferroelectric ceramic material has a chemical formula of Ag1- xNaxNbO3，0<x≤0.5。
One of the purposes of the invention is to provide a silver niobate-based antiferroelectric ceramic material, namely a sodium-doped silver niobate-based antiferroelectric ceramic material Ag1-xNaxNbO3(0<x is less than or equal to 0.5). After the silver niobate-based antiferroelectric ceramic material is doped with Na, the remanent polarization can be reduced, and the phase change electric field intensity can be improved, so that the energy storage density can be improved, and the specific mechanism is as follows: the effective energy storage density of the antiferroelectric material is determined by the saturation polarization strength, the remanent polarization strength and the ferroelectric-antiferroelectric phase transformation electric field, the larger the saturation polarization strength is, the smaller the remanent polarization strength is, the larger the ferroelectric-antiferroelectric phase transformation electric field is, the larger the effective energy storage density is, after the doping of Na, the radius of sodium ions is smaller than that of silver ions, so that the tolerance factor is reduced, the antiferroelectric phase is easier to stabilize, the remanent polarization strength is reduced, the ferroelectric-antiferroelectric phase transformation electric field strength is improved, and the effective energy storage density is improved. In addition, the Na doping can also reduce the cost. The protection range of the invention is not limited to single doped Na ions, other metal ions or a plurality of metal ions are codoped, the residual polarization is reduced, and the energy storage density of the silver niobate-based ceramic material can be still improved under the condition of improving the phase change electric field.
As a preferable scheme:
according to the silver niobate-based antiferroelectric ceramic material, the effective energy storage density (the effective energy storage density can be calculated by integrating the original data according to the area enclosed by the upper half part of the ferroelectric hysteresis loop and the Y axis in the polarization-electric field relation curve) of the silver niobate-based antiferroelectric ceramic material is 1.3-1.8J/cm3The effective energy storage density is not limited to the range, and can be further improved by further adjusting the formula and the process.
The silver niobate-based antiferroelectric ceramic material has a plurality of phase changes from room temperature to the temperature, wherein the phase changes are rhombic-oriented orthorhombic phases M1Rhombohedral oriented orthogonal phase M2Rhombohedral oriented orthogonal phase M3And a parallel oriented orthogonal phase O, there being a dielectric peak at the phase transition point.
The silver niobate-based antiferroelectric ceramic material has an antiferroelectric phase stability temperature range (obtained by testing impedance by using an impedance analyzer) of 81-426 ℃. The stable antiferroelectric phase temperature range of the silver niobate-based antiferroelectric ceramic material in the prior art is 60-350 ℃, and compared with the prior art, the antiferroelectric ceramic material has a wider antiferroelectric phase region.
The invention also provides a method for preparing the silver niobate-based antiferroelectric ceramic material, which comprises the following steps:
the method comprises the following steps: ag2Preparing O powder;
slowly adding AgNO into NaOH solution by multiple times under stirring3A solution; filtering and drying after reaction to obtain Ag2O, grinding into powder;
step two: carrying out hydrothermal reaction;
preparing NH with the concentration of 1.6mol/L by using deionized water4H2F solution, adding Ag slowly2O powder, NaOH powder and Nb2O5Heating the powder to carry out hydrothermal reaction;
Ag2O、NaOH、Nb2O5and NH4H2The molar ratio of F is (1-x) x:1: y, deionized water and NH4H2The molar ratio of F is 30-40: 1; wherein 0<x≤0.5，y≥2；
Step three: granulating;
sequentially carrying out suction filtration washing, drying, grinding and sieving on a product of the hydrothermal reaction to obtain screened powder, adding a binder into the screened powder, granulating, and sieving for the second time to obtain granules;
step four: preparing a ceramic blank;
carrying out pressure molding on the granules of the granulated material to obtain a ceramic blank;
step five: sintering the ceramic;
performing plastic removal on the ceramic blank at the temperature of 600-900 ℃ for 1-3 hours, and sintering at the temperature of 1000-1100 ℃ for 2-4 hours to form a ceramic;
thus obtaining the silver niobate-based antiferroelectric ceramic material.
The invention also solves the problem that the solid phase preparation technology in the prior art needs oxygen introduction sintering to obtain pure phase materials. The invention also aims to provide a method for preparing the single-phase silver niobate-based antiferroelectric ceramic material without introducing oxygen, and silver nitrate AgNO is utilized3Powder, NaOH powder, Nb2O5Powder and NH4HF2The powder is used as a raw material, pure-phase powder is firstly synthesized by a hydrothermal method, and the antiferroelectric silver niobate and sodium-doped silver niobate ceramic materials are further sintered in the air. The scope of the present invention is not limited to hydrothermal synthesis, but other wet chemical synthesis methods, such as synthesizing silver niobate-based powder in advance, can also be used as a method for preparing silver niobate-based ceramic materials.
As a preferable scheme:
the method as described above, step one, AgNO3The concentration of the solution is 0.4-0.6 mol/L, the concentration of the NaOH solution is 0.2-0.4 mol/L, AgNO3The molar ratio of the NaOH solution to the NaOH solution is 1: 1; the stirring condition is magnetic stirring; and washing with deionized water during suction filtration, wherein the drying temperature is 60-90 ℃, and the drying time is 6-10 hours.
According to the method, in the second step, the temperature of the hydrothermal reaction is 150-210 ℃, and the time of the hydrothermal reaction is 24-50 hours; the hydrothermal reaction is carried out in a reaction kettle with a polytetrafluoroethylene lining.
According to the method, in the third step, the screened powder obtained by screening is screened by using a mesh screen of 40-100 meshes; the secondary screening uses a mesh screen of 40-100 meshes; the binder is polyvinyl alcohol sol or polyvinyl butyral sol, and the addition amount of the binder is 3-8% of the mass of the screened powder;
in the fourth step, the pressure forming means pressing the blank body by a dry pressing forming machine, wherein the pressure is 100-500 MPa.
The invention also provides an application of the silver niobate-based antiferroelectric ceramic material, and the silver niobate-based antiferroelectric ceramic material is subjected to surface polishing, silver paste printing and silver firing at the temperature of 500-700 ℃ to prepare the silver niobate-based antiferroelectric ceramic capacitor.
The invention also aims to provide a silver niobate-based antiferroelectric ceramic capacitor, which is a sodium-doped silver niobate-based antiferroelectric ceramic capacitor and has higher effective energy storage density.
Advantageous effects
Compared with the prior art method, the method has the advantages that the oxygen atmosphere required in the sintering process is avoided, and the traditional solid phase method uses Ag2O raw material is directly sintered, and Ag2O can be decomposed into Ag simple substance and O at 100-300 DEG C2In order to avoid the reaction which generally needs to be sintered in an oxygen atmosphere, the invention firstly uses a hydrothermal method to synthesize the silver niobate powder, solves the problem that oxygen needs to be introduced in the sintering process, thereby obtaining a pure product, simplifying the complexity of the sintering process and improving the purity and the performance of the prepared ceramic.
Compared with the prior art, the method has the advantages that the effective energy storage density of the silver niobate-based antiferroelectric ceramic material is improved, the silver niobate has higher remanent polarization and lower phase-change electric field intensity, so that the effective energy storage density is not high, the remanent polarization can be reduced by adopting Na doping, the phase-change electric field intensity is improved, so that the effective energy storage density can be improved, and in addition, the cost can be reduced by adopting Na doping.
The method has the advantages of simple process, easily obtained raw materials, controllable product and good repeatability, and can be widely used for preparing the lead-free antiferroelectric silver niobate-based material and further researching the structural performance of the lead-free antiferroelectric silver niobate-based material.
Drawings
FIG. 1 shows Agx-1NaxNbO3X-ray diffraction pattern of the powder;
FIG. 2 is a plot of polarization-electric field relationship for a silver niobate-based antiferroelectric ceramic material;
FIG. 3 is a graph showing the change of dielectric constant with temperature of the silver niobate-based antiferroelectric ceramic material prepared in comparative example 1;
fig. 4 is a graph showing the change of dielectric constant with temperature of the silver niobate-based antiferroelectric ceramic material prepared in example 1.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The invention relates to a silver niobate-based antiferroelectric ceramic material with a chemical formula of Ag1-xNaxNbO3，0<x≤0.5；
The effective energy storage density of the silver niobate-based antiferroelectric ceramic material is 1.3-1.8J/cm3；
The silver niobate-based antiferroelectric ceramic material has multiple phase changes along with the rise of temperature, and the phase changes are respectively rhombic oriented orthorhombic phase M1Rhombohedral oriented orthogonal phase M2Rhombohedral oriented orthogonal phase M3And a parallel oriented orthogonal phase O, having a dielectric peak at the phase transition point;
the stable antiferroelectric phase temperature range of the silver niobate-based antiferroelectric ceramic material is 81-426 ℃.
Example 1
A preparation method of silver niobate-based antiferroelectric ceramic material comprises the following steps:
the method comprises the following steps: ag2Preparing O powder;
under the condition of magnetic stirring, AgNO with the concentration of 0.5mol/L is slowly added into NaOH solution with the concentration of 0.3mol/L for a plurality of times3Solution of AgNO3The molar ratio of the NaOH solution to the NaOH solution is 1: 1; filtering and drying after reaction to obtain Ag2Grinding into powder, washing with deionized water during suction filtration, and drying at 70 deg.C for a certain time8 hours;
step two: carrying out hydrothermal reaction;
preparing NH with the concentration of 1.6mol/L by using deionized water4H2F solution, adding Ag slowly2O powder, NaOH powder and Nb2O5Mixing the raw materials, stirring for 10-30 minutes until the raw materials are uniform, heating to 200 ℃ for hydrothermal reaction, wherein the hydrothermal reaction time is 48 hours, the hydrothermal reaction is carried out in a reaction kettle with a polytetrafluoroethylene lining, and the filling degree is 70%;
Ag2O、NaOH、Nb2O5and NH4H2The molar ratio of F is (1-x) x:1: y, deionized water and NH4H2The molar ratio of F is 33:1, x is 0.2, and y is 3;
the dielectric material (Ag) obtained in example 1 was usedx-1NaxNbO3Powder) is subjected to XRD test, the test result is shown in figure 1, the medium material is in a cubic phase structure at room temperature, and no second phase is observed;
step three: granulating;
sequentially carrying out suction filtration washing, drying, grinding and sieving with a 80-mesh sieve to obtain screened powder, then adding a binder into the screened powder for granulation, and sieving with a 50-mesh sieve to obtain granules, wherein the binder is polyvinyl alcohol sol, and the addition amount of the binder is 5% of the mass of the screened powder;
step four: preparing a ceramic blank;
aging the granules of the granulating material for 24h, putting the granules into a stainless steel mold with the diameter of 10mm, and pressing the granules into a green body by using a dry pressing forming machine to obtain a ceramic green body, wherein the pressure is 300 MPa;
step five: sintering the ceramic;
performing plastic removal on the ceramic blank at the temperature of 800 ℃ for 2 hours, and sintering at the temperature of 1050 ℃ for 3 hours to form ceramic;
the silver niobate-based antiferroelectric ceramic material is obtained, and the chemical formula of the silver niobate-based antiferroelectric ceramic material is Ag1- xNaxNbO3The effective energy storage density of the silver niobate-based antiferroelectric ceramic material is 1.8J/cm3The silver niobate-based antiferroelectric ceramic material has multiple phase changes along with the rise of temperature, and the phase changes are respectively rhombic oriented orthorhombic phase M1Rhombohedral oriented orthogonal phase M2Rhombohedral oriented orthogonal phase M3And a parallel-oriented orthogonal phase O, wherein a dielectric peak exists at a phase change point, and the antiferroelectric phase stability temperature range of the silver niobate-based antiferroelectric ceramic material is 81-426 ℃.
The ceramic material prepared in example 1 was subjected to a polarization-electric field relationship test, as shown in FIG. 2, which is a typical antiferroelectric double hysteresis loop, and the effective energy storage density calculated therefrom was 1.8J/cm3；
The ceramic material obtained in example 1 was subjected to a dielectric temperature spectrum test, as shown in FIG. 4, in which M was clearly present1、M2、M3And the phase change dielectric anomaly between the O phase and the ceramic material prepared by the solid phase method.
The whole antiferroelectric phase region is wider than the ceramic material (70-350 ℃) prepared by the solid phase method from 81 ℃ to 426 ℃.
Comparative example 1
A preparation method of silver niobate-based antiferroelectric ceramic material comprises the following steps:
the method comprises the following steps: carrying out hydrothermal reaction;
preparing NH with the concentration of 1.6mol/L by using deionized water4H2F solution, adding Ag slowly2O powder and Nb2O5Mixing the raw materials, stirring for 10-30 minutes until the raw materials are uniform, heating to 200 ℃ for hydrothermal reaction, wherein the hydrothermal reaction time is 44 hours, the hydrothermal reaction is carried out in a reaction kettle with a polytetrafluoroethylene lining, and the filling degree is 70%;
Ag2O、Nb2O5and NH4H2The molar ratio of F is (1-x) to 1: y, deionized water to NH4H2The molar ratio of F is 33:1, x is 0, and y is 3;
the dielectric material (Ag) obtained in comparative example 1 was usedx-1NaxNbO3Powder) is subjected to XRD test, the test result is shown in figure 1, the medium material is in a cubic phase structure at room temperature, and no second phase is observed;
step two: granulating;
sequentially carrying out suction filtration washing, drying, grinding and sieving with a 80-mesh sieve to obtain screened powder, then adding a binder into the screened powder for granulation, and sieving with a 50-mesh sieve to obtain granules, wherein the binder is polyvinyl alcohol sol, and the addition amount of the binder is 5% of the mass of the screened powder;
step three: preparing a ceramic blank;
aging the granules of the granulating material for 24h, putting the granules into a stainless steel mold with the diameter of 10mm, and pressing the granules into a green body by using a dry pressing forming machine to obtain a ceramic green body, wherein the pressure is 300 MPa;
step four: sintering the ceramic;
heating the ceramic blank to 800 ℃ at the speed of 3 ℃/min, performing plastic removal for 2 hours, heating to 1050 ℃ at the speed of 5 ℃/min, sintering for 3 hours, and cooling at the speed of 5 ℃/min to obtain ceramic;
the silver niobate-based antiferroelectric ceramic material is obtained, and the chemical formula of the silver niobate-based antiferroelectric ceramic material is Ag1- xNaxNbO3The effective energy storage density of the silver niobate-based antiferroelectric ceramic material is 1.4J/cm3The silver niobate-based antiferroelectric ceramic material has multiple phase changes along with the rise of temperature, and the phase changes are respectively rhombic oriented orthorhombic phase M1Rhombohedral oriented orthogonal phase M2Rhombohedral oriented orthogonal phase M3And a parallel-oriented orthogonal phase O, wherein a dielectric peak exists at a phase change point, and the antiferroelectric phase stability temperature range of the silver niobate-based antiferroelectric ceramic material is 78-410 ℃.
The ceramic material prepared in comparative example 1 was subjected to a polarization-electric field relationship test, as shown in FIG. 2, which is a typical antiferroelectric double hysteresis loop, and the effective energy storage density calculated therefrom was 1.4J/cm3；
The ceramic material obtained in comparative example 1 was subjected to a dielectric temperature spectrum test, as shown in FIG. 3, in which M was clearly present1、M2、M3And the phase change dielectric anomaly between the O phase and the ceramic material prepared by the solid phase method is similar to that of the ceramic material prepared by the solid phase method;
the whole antiferroelectric phase region is wider than the ceramic material (70-350 ℃) prepared by the solid phase method from 78 ℃ to 410 ℃.
Comparative example 2
A preparation method of silver niobate-based antiferroelectric ceramic material comprises the following steps:
the method comprises the following steps: carrying out hydrothermal reaction;
preparing NH with the concentration of 1.6mol/L by using deionized water4H2F solution, adding Ag slowly2O powder and Nb2O5Mixing the raw materials, stirring for 10-30 minutes to be uniform, heating to 200 ℃ for hydrothermal reaction for 24 hours, and carrying out the hydrothermal reaction in a reaction kettle with a polytetrafluoroethylene lining;
Ag2O、Nb2O5and NH4H2The molar ratio of F is (1-x) to 1: y, deionized water to NH4H2The molar ratio of F is 50:1, x is 0, and y is 2;
the dielectric material (Ag) obtained in comparative example 2 was usedx-1NaxNbO3Powder) is subjected to XRD test, the test result is shown in figure 1, the medium material is in a cubic phase structure at room temperature, but the generation of a second phase is observed;
step two: granulating;
sequentially carrying out suction filtration washing, drying, grinding and sieving with a 80-mesh sieve to obtain screened powder, then adding a binder into the screened powder for granulation, and sieving with a 50-mesh sieve to obtain granules, wherein the binder is polyvinyl alcohol sol, and the addition amount of the binder is 5% of the mass of the screened powder;
step three: preparing a ceramic blank;
aging the granules of the granulating material for 24h, putting the granules into a stainless steel mold with the diameter of 10mm, and pressing the granules into a green body by using a dry pressing forming machine to obtain a ceramic green body, wherein the pressure is 300 MPa;
step four: sintering the ceramic;
placing the ceramic blank into a sintering furnace, heating to 800 ℃ at the speed of 3 ℃/minute, performing plastic removal for 2 hours, heating to 1050 ℃ at the speed of 5 ℃/minute, sintering for 3 hours, and cooling to room temperature at the speed of 5 ℃/minute;
the silver niobate-based antiferroelectric ceramic material is obtained, and the chemical formula of the silver niobate-based antiferroelectric ceramic material is shown in the specificationAg1- xNaxNbO3。
As can be seen from example 1, comparative example 2, and fig. 1 to 4, the pure-phase silver niobate antiferroelectric ceramic material and the sodium-doped silver niobate antiferroelectric ceramic material can be obtained using a reasonable hydrothermal time, which can effectively solve the problem of decomposition of the solid-phase method raw material, and the preparation process does not require oxygen introduction, thereby simplifying the preparation technology. After the Na is doped, the stable temperature range of the antiferroelectric phase can be further expanded, and the effective energy storage density is improved.
Example 2
A preparation method of silver niobate-based antiferroelectric ceramic material comprises the following steps:
the method comprises the following steps: ag2Preparing O powder;
under the condition of magnetic stirring, AgNO with the concentration of 0.4mol/L is slowly added into NaOH solution with the concentration of 0.4mol/L for a plurality of times3Solution of AgNO3The molar ratio of the NaOH solution to the NaOH solution is 1: 1; filtering and drying after reaction to obtain Ag2Grinding the mixture into powder, washing the powder by using deionized water during suction filtration, and drying the powder at the temperature of 60 ℃ for 10 hours;
step two: carrying out hydrothermal reaction;
preparing NH with the concentration of 1.6mol/L by using deionized water4H2F solution, adding Ag slowly2O powder, NaOH powder and Nb2O5Heating the powder to 150 ℃ to carry out hydrothermal reaction for 48 hours, wherein the hydrothermal reaction is carried out in a reaction kettle with a polytetrafluoroethylene lining;
Ag2O、NaOH、Nb2O5and NH4H2The molar ratio of F is (1-x) x:1: y, deionized water and NH4H2The molar ratio of F is 30:1, x is 0.5, and y is 2;
step three: granulating;
sequentially carrying out suction filtration, washing, drying, grinding and screening on a product of the hydrothermal reaction by a 40-mesh screen to obtain screened powder, then adding a binder into the screened powder for granulation, and screening by a 40-mesh screen to obtain granules, wherein the binder is polyvinyl butyral sol, and the addition amount of the binder is 6% of the mass of the screened powder;
step four: preparing a ceramic blank;
pressing the granules of the granulating material into a green body by using a dry pressing forming machine to obtain a ceramic green body, wherein the pressure is 500 MPa;
step five: sintering the ceramic;
performing plastic removal on the ceramic blank at the temperature of 750 ℃ for 3 hours, and sintering at the temperature of 1100 ℃ for 2 hours to form ceramic;
the silver niobate-based antiferroelectric ceramic material is obtained, and the chemical formula of the silver niobate-based antiferroelectric ceramic material is Ag1- xNaxNbO3The effective energy storage density of the silver niobate-based antiferroelectric ceramic material is 1.3J/cm3The silver niobate-based antiferroelectric ceramic material has multiple phase changes along with the rise of temperature, and the phase changes are respectively rhombic oriented orthorhombic phase M1Rhombohedral oriented orthogonal phase M2Rhombohedral oriented orthogonal phase M3And a parallel-oriented orthogonal phase O, wherein a dielectric peak exists at a phase change point, and the antiferroelectric phase stability temperature range of the silver niobate-based antiferroelectric ceramic material is 81-426 ℃.
Example 3
A preparation method of silver niobate-based antiferroelectric ceramic material comprises the following steps:
the method comprises the following steps: ag2Preparing O powder;
under the condition of magnetic stirring, AgNO with the concentration of 0.6mol/L is slowly added into NaOH solution with the concentration of 0.3mol/L for a plurality of times3Solution of AgNO3The molar ratio of the NaOH solution to the NaOH solution is 1: 1; filtering and drying after reaction to obtain Ag2Grinding the mixture into powder, washing the powder by using deionized water during suction filtration, and drying the powder at the temperature of 90 ℃ for 8 hours;
step two: carrying out hydrothermal reaction;
preparing NH with the concentration of 1.6mol/L by using deionized water4H2F solution, adding Ag slowly2O powder, NaOH powder and Nb2O5Heating the powder to 182 ℃ to carry out hydrothermal reaction for 35 hours, wherein the hydrothermal reaction is carried out in a reaction kettle with a polytetrafluoroethylene lining;
Ag2O、NaOH、Nb2O5and NH4H2The molar ratio of F is (1-x) x:1: y, deionized water and NH4H2The molar ratio of F is 40:1, x is 0.2, and y is 4;
step three: granulating;
sequentially carrying out suction filtration washing, drying, grinding and sieving with a 100-mesh sieve to obtain screened powder, then adding a binder into the screened powder for granulation, and sieving with a 80-mesh sieve to obtain a granulated material, wherein the binder is polyvinyl butyral sol, and the addition amount of the binder is 7% of the mass of the screened powder;
step four: preparing a ceramic blank;
pressing the granules of the granulating material into a green body by using a dry pressing forming machine to obtain a ceramic green body, wherein the pressure is 100 MPa;
step five: sintering the ceramic;
performing plastic removal on the ceramic blank at the temperature of 600 ℃ for 1 hour, and sintering at the temperature of 1100 ℃ for 4 hours to form ceramic;
the silver niobate-based antiferroelectric ceramic material is obtained, and the chemical formula of the silver niobate-based antiferroelectric ceramic material is Ag1- xNaxNbO3The effective energy storage density of the silver niobate-based antiferroelectric ceramic material is 1.7J/cm3The silver niobate-based antiferroelectric ceramic material has multiple phase changes along with the rise of temperature, and the phase changes are respectively rhombic oriented orthorhombic phase M1Rhombohedral oriented orthogonal phase M2Rhombohedral oriented orthogonal phase M3And a parallel-oriented orthogonal phase O, wherein a dielectric peak exists at a phase change point, and the antiferroelectric phase stability temperature range of the silver niobate-based antiferroelectric ceramic material is 81-426 ℃.
Example 4
A preparation method of silver niobate-based antiferroelectric ceramic material comprises the following steps:
the method comprises the following steps: ag2Preparing O powder;
under the condition of magnetic stirring, AgNO with the concentration of 0.5mol/L is slowly added into NaOH solution with the concentration of 0.2mol/L for a plurality of times3Solution of AgNO3The molar ratio of the NaOH solution to the NaOH solution is 1: 1; filtering and drying after reaction to obtain Ag2Grinding the mixture into powder, washing the powder by using deionized water during suction filtration, and drying the powder at the temperature of 75 ℃ for 9 hours;
step two: carrying out hydrothermal reaction;
preparing NH with the concentration of 1.6mol/L by using deionized water4H2F solution, adding Ag slowly2O powder, NaOH powder and Nb2O5Heating the powder to 210 ℃ for hydrothermal reaction for 50 hours, wherein the hydrothermal reaction is carried out in a reaction kettle with a polytetrafluoroethylene lining;
Ag2O、NaOH、Nb2O5and NH4H2The molar ratio of F is (1-x) x:1: y, deionized water and NH4H2The molar ratio of F is 35:1, x is 0.3, and y is 5;
step three: granulating;
sequentially carrying out suction filtration washing, drying, grinding and sieving with a 95-mesh sieve to obtain screened powder, then adding a binder into the screened powder for granulation, and sieving with a 100-mesh sieve to obtain a granulated material, wherein the binder is polyvinyl butyral sol, and the addition amount of the binder is 8% of the mass of the screened powder;
step four: preparing a ceramic blank;
pressing the granules of the granulating material into a green body by using a dry pressing forming machine to obtain a ceramic green body, wherein the pressure is 250 MPa;
step five: sintering the ceramic;
performing plastic removal on the ceramic blank at the temperature of 900 ℃ for 2 hours, and sintering at the temperature of 1080 ℃ for 3 hours to form ceramic;
the silver niobate-based antiferroelectric ceramic material is obtained, and the chemical formula of the silver niobate-based antiferroelectric ceramic material is Ag1- xNaxNbO3The effective energy storage density of the silver niobate-based antiferroelectric ceramic material is 1.6J/cm3The silver niobate-based antiferroelectric ceramic material has multiple phase changes along with the rise of temperature, and the phase changes are respectively rhombic oriented orthorhombic phase M1Rhombohedral oriented orthogonal phase M2Rhombohedral oriented orthogonal phase M3And a parallel oriented orthogonal phase O, a dielectric peak existing at the phase transition point, a silver niobate base inverseThe stable temperature range of the antiferroelectric phase of the ferroelectric ceramic material is 81-426 ℃.
Example 5
A preparation method of silver niobate-based antiferroelectric ceramic material comprises the following steps:
the method comprises the following steps: ag2Preparing O powder;
under the condition of magnetic stirring, AgNO with the concentration of 0.5mol/L is slowly added into NaOH solution with the concentration of 0.3mol/L for a plurality of times3Solution of AgNO3The molar ratio of the NaOH solution to the NaOH solution is 1: 1; filtering and drying after reaction to obtain Ag2Grinding the mixture into powder, washing the powder by using deionized water during suction filtration, and drying the powder at the temperature of 75 ℃ for 6 hours;
step two: carrying out hydrothermal reaction;
preparing NH with the concentration of 1.6mol/L by using deionized water4H2F solution, adding Ag slowly2O powder, NaOH powder and Nb2O5Heating the powder to 179 ℃ for hydrothermal reaction for 37 hours, wherein the hydrothermal reaction is carried out in a reaction kettle with a polytetrafluoroethylene lining;
Ag2O、NaOH、Nb2O5and NH4H2The molar ratio of F is (1-x) x:1: y, deionized water and NH4H2The molar ratio of F is 32:1, x is 0.1, and y is 4;
step three: granulating;
sequentially carrying out suction filtration washing, drying, grinding and screening on a product of the hydrothermal reaction by using a 75-mesh screen to obtain screened powder, then adding a binder into the screened powder for granulation, and screening by using a 75-mesh screen to obtain a granulated material, wherein the binder is polyvinyl alcohol sol, and the addition amount of the polyvinyl alcohol sol is 3% of the mass of the screened powder;
step four: preparing a ceramic blank;
pressing the granules of the granulating material into a green body by using a dry pressing forming machine to obtain a ceramic green body, wherein the pressure is 320 MPa;
step five: sintering the ceramic;
performing plastic removal on the ceramic blank at the temperature of 750 ℃ for 2 hours, and sintering at the temperature of 1050 ℃ for 3 hours to form ceramic;
the silver niobate-based antiferroelectric ceramic material is obtained, and the chemical formula of the silver niobate-based antiferroelectric ceramic material is Ag1- xNaxNbO3The effective energy storage density of the silver niobate-based antiferroelectric ceramic material is 1.6J/cm3The silver niobate-based antiferroelectric ceramic material has multiple phase changes along with the rise of temperature, and the phase changes are respectively rhombic oriented orthorhombic phase M1Rhombohedral oriented orthogonal phase M2Rhombohedral oriented orthogonal phase M3And a parallel-oriented orthogonal phase O, wherein a dielectric peak exists at a phase change point, and the antiferroelectric phase stability temperature range of the silver niobate-based antiferroelectric ceramic material is 81-426 ℃.
Example 6
An application of the silver niobate-based antiferroelectric ceramic material is that the silver niobate-based antiferroelectric ceramic material prepared in the embodiment 1 is subjected to surface polishing, silver paste printing and silver firing for 30min at the temperature of 600 ℃, so that the silver niobate-based antiferroelectric ceramic capacitor is prepared.
Example 7
An application of the silver niobate-based antiferroelectric ceramic material is that the silver niobate-based antiferroelectric ceramic material prepared in the embodiment 2 is subjected to surface polishing, silver paste printing and silver firing for 30min at the temperature of 600 ℃, so that the silver niobate-based antiferroelectric ceramic capacitor is prepared.
Example 8
An application of the silver niobate-based antiferroelectric ceramic material is that the silver niobate-based antiferroelectric ceramic material prepared in the embodiment 3 is subjected to surface polishing, silver paste printing and silver firing for 30min at the temperature of 700 ℃, so that the silver niobate-based antiferroelectric ceramic capacitor is prepared.
Example 9
An application of the silver niobate-based antiferroelectric ceramic material is that the silver niobate-based antiferroelectric ceramic material prepared in the embodiment 4 is subjected to surface polishing, silver paste printing and silver firing for 30min at the temperature of 500 ℃, so that the silver niobate-based antiferroelectric ceramic capacitor is prepared.
Claims (9)
1. A silver niobate-based antiferroelectric ceramic material is characterized in that: the chemical formula of the silver niobate-based antiferroelectric ceramic material is Ag1-xNaxNbO3，0<x≤0.5。
2. The silver niobate-based antiferroelectric ceramic material according to claim 1, wherein the effective energy storage density of the silver niobate-based antiferroelectric ceramic material is 1.3 to 1.8J/cm3。
3. The silver niobate-based antiferroelectric ceramic material of claim 1, wherein the silver niobate-based antiferroelectric ceramic material exhibits a plurality of phase changes with increasing temperature, each being a rhombohedral orthogonal phase M1Rhombohedral oriented orthogonal phase M2Rhombohedral oriented orthogonal phase M3And a parallel oriented orthogonal phase O, there being a dielectric peak at the phase transition point.
4. The silver niobate-based antiferroelectric ceramic material according to claim 1, wherein the antiferroelectric phase stability temperature of the silver niobate-based antiferroelectric ceramic material is in a range of 81 to 426 ℃.
5. A method for preparing a silver niobate-based antiferroelectric ceramic material according to any one of claims 1 to 4, comprising the steps of:
the method comprises the following steps: ag2Preparing O powder;
adding AgNO into NaOH solution for multiple times under stirring3A solution; filtering and drying after reaction to obtain Ag2O, grinding into powder;
step two: carrying out hydrothermal reaction;
preparing NH with the concentration of 1.6mol/L by using deionized water4H2F solution, adding Ag2O powder, NaOH powder and Nb2O5Heating the powder to carry out hydrothermal reaction;
Ag2O、NaOH、Nb2O5and NH4H2The molar ratio of F is (1-x) x:1: y, deionized water and NH4H2The molar ratio of F is 30-40: 1; wherein 0<x≤0.5，y≥2；
Step three: granulating;
sequentially carrying out suction filtration washing, drying, grinding and sieving on a product of the hydrothermal reaction to obtain screened powder, adding a binder into the screened powder, granulating, and sieving for the second time to obtain granules; step four: preparing a ceramic blank;
carrying out pressure molding on the granules of the granulated material to obtain a ceramic blank; step five: sintering the ceramic;
performing plastic removal on the ceramic blank at the temperature of 600-900 ℃ for 1-3 hours, and sintering at the temperature of 1000-1100 ℃ for 2-4 hours to form a ceramic;
thus obtaining the silver niobate-based antiferroelectric ceramic material.
6. The method of claim 5, wherein in step one, AgNO3The concentration of the solution is 0.4-0.6 mol/L, the concentration of the NaOH solution is 0.2-0.4 mol/L, AgNO3The molar ratio of the NaOH solution to the NaOH solution is 1: 1; the stirring condition is magnetic stirring; and washing with deionized water during suction filtration, wherein the drying temperature is 60-90 ℃, and the drying time is 6-10 hours.
7. The method according to claim 5, wherein in the second step, the temperature of the hydrothermal reaction is 150-210 ℃, and the time of the hydrothermal reaction is 24-50 hours; the hydrothermal reaction is carried out in a reaction kettle with a polytetrafluoroethylene lining.
8. The method according to claim 5, characterized in that in the third step, the screened powder obtained by screening uses a 40-100 mesh screen; the secondary screening uses a mesh screen of 40-100 meshes; the binder is polyvinyl alcohol sol or polyvinyl butyral sol, and the addition amount of the binder is 3-8% of the mass of the screened powder;
in the fourth step, the pressure forming means pressing the blank body by a dry pressing forming machine, wherein the pressure is 100-500 MPa.
9. The use of a silver niobate-based antiferroelectric ceramic material according to any one of claims 1 to 4, wherein: and (2) polishing the surface of the silver niobate-based antiferroelectric ceramic material, printing silver paste, and burning silver at the temperature of 500-700 ℃ to obtain the silver niobate-based antiferroelectric ceramic capacitor.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51120000A (en) * | 1975-04-11 | 1976-10-20 | Taiyo Yuden Co Ltd | Piezo-electric ceramic composition |
| CN1793034A (en) * | 2005-11-16 | 2006-06-28 | 天津大学 | Chemical preparation process for high dielectric porcelain material |
| US20070138917A1 (en) * | 2003-05-23 | 2007-06-21 | Schultz Jeffrey P | Ferroelastic ceramic-reinforced metal matrix composites |
| EP2138472A2 (en) * | 2007-02-26 | 2009-12-30 | Ngk Insulators, Ltd. | Plate-like polycrystalline particle, method for producing plate-like polycrystalline particles, and method for producing crystallographically-oriented ceramic |
| US20120328878A1 (en) * | 2009-11-26 | 2012-12-27 | Hitachi Metals, Ltd. | Anisotropically shaped powder and method for producing the same |
| US20130306902A1 (en) * | 2011-02-04 | 2013-11-21 | H.C. Starck Gmbh | Process for producing a pure-phase multisubstance system, a ceramic material based on the pure-phase multisubstance system, a shaped body, and a composite formed therefrom |
| CN103482976A (en) * | 2013-09-05 | 2014-01-01 | 中国科学院声学研究所 | Lead zirconate titanate-based piezoelectric material for ultrasonic well logging and preparation method thereof |
| US20150144588A1 (en) * | 2013-11-22 | 2015-05-28 | Sandia Corporation | Voltage Tunability of Thermal Conductivity in Ferroelectric Materials |
| CN105777117A (en) * | 2015-12-29 | 2016-07-20 | 上海工程技术大学 | Lithium tantalate-based composite ceramic and preparation method thereof |
| CN106478097A (en) * | 2016-09-22 | 2017-03-08 | 清华大学 | Silver niobate-based lead-free anti-ferroelectric energy storage ceramic and preparation method thereof |
| CN109650885A (en) * | 2018-12-11 | 2019-04-19 | 中国科学院上海硅酸盐研究所 | One kind mixing lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material and preparation method thereof |
| CN109704762A (en) * | 2019-02-22 | 2019-05-03 | 中国科学院上海硅酸盐研究所 | A kind of SrNb2 O6 base class antiferroelectric ceramics and its preparation method and application |
-
2020
- 2020-04-17 CN CN202010303320.XA patent/CN111517787A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51120000A (en) * | 1975-04-11 | 1976-10-20 | Taiyo Yuden Co Ltd | Piezo-electric ceramic composition |
| US20070138917A1 (en) * | 2003-05-23 | 2007-06-21 | Schultz Jeffrey P | Ferroelastic ceramic-reinforced metal matrix composites |
| CN1793034A (en) * | 2005-11-16 | 2006-06-28 | 天津大学 | Chemical preparation process for high dielectric porcelain material |
| EP2138472A2 (en) * | 2007-02-26 | 2009-12-30 | Ngk Insulators, Ltd. | Plate-like polycrystalline particle, method for producing plate-like polycrystalline particles, and method for producing crystallographically-oriented ceramic |
| US20120328878A1 (en) * | 2009-11-26 | 2012-12-27 | Hitachi Metals, Ltd. | Anisotropically shaped powder and method for producing the same |
| US20130306902A1 (en) * | 2011-02-04 | 2013-11-21 | H.C. Starck Gmbh | Process for producing a pure-phase multisubstance system, a ceramic material based on the pure-phase multisubstance system, a shaped body, and a composite formed therefrom |
| CN103482976A (en) * | 2013-09-05 | 2014-01-01 | 中国科学院声学研究所 | Lead zirconate titanate-based piezoelectric material for ultrasonic well logging and preparation method thereof |
| US20150144588A1 (en) * | 2013-11-22 | 2015-05-28 | Sandia Corporation | Voltage Tunability of Thermal Conductivity in Ferroelectric Materials |
| CN105777117A (en) * | 2015-12-29 | 2016-07-20 | 上海工程技术大学 | Lithium tantalate-based composite ceramic and preparation method thereof |
| CN106478097A (en) * | 2016-09-22 | 2017-03-08 | 清华大学 | Silver niobate-based lead-free anti-ferroelectric energy storage ceramic and preparation method thereof |
| CN109650885A (en) * | 2018-12-11 | 2019-04-19 | 中国科学院上海硅酸盐研究所 | One kind mixing lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material and preparation method thereof |
| CN109704762A (en) * | 2019-02-22 | 2019-05-03 | 中国科学院上海硅酸盐研究所 | A kind of SrNb2 O6 base class antiferroelectric ceramics and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| A KANIA: "Ag1-xNaxNbO3 (ANN) solid solutions: from disordered antiferroelectric AgNbO3 to normal antiferroelectric NaNbO3", 《JOURNAL OF PHYSICS-CONDENSED MATERIAL》 * |
| ZHUOZHUANG XIE: "A novel method of preparing antiferroelectric silver niobate AgNbO3 Ceramics", 《CERAMICS INTERNATIONAL》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024248A (en) * | 2021-03-03 | 2021-06-25 | 佛山科学技术学院 | Antiferroelectric ceramic and preparation method thereof |
| CN113638046A (en) * | 2021-08-16 | 2021-11-12 | 山东省科学院新材料研究所 | Antiferroelectric AgNbO3Preparation method and application of crystal |
| CN114907123A (en) * | 2022-06-17 | 2022-08-16 | 陕西科技大学 | A-site disubstituted silver niobate-based perovskite antiferroelectric ceramic material and preparation method thereof |
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