CN113698203A - Yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material and preparation method thereof - Google Patents

Yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material and preparation method thereof Download PDF

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CN113698203A
CN113698203A CN202110990105.6A CN202110990105A CN113698203A CN 113698203 A CN113698203 A CN 113698203A CN 202110990105 A CN202110990105 A CN 202110990105A CN 113698203 A CN113698203 A CN 113698203A
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ceramic material
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yttrium
hafnium
silver niobate
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CN113698203B (en
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薛人中
朱祥
赵承周
李涛
代海洋
刘德伟
陈思源
陈红炫
崔梦茹
白新涛
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Zhengzhou University of Light Industry
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Abstract

The invention discloses a silver niobate-based antiferroelectric ceramic material, which has a chemical formula of Ag x1‑3Y x Nb x1‑Hf x O3X is more than or equal to 0 and less than or equal to 0.10, preferably more than or equal to 0.03 and less than or equal to 0.05, and has the characteristic of electric field induced antiferroelectric-ferroelectric phase transition. The process reduces the high-temperature sintering time of the silver niobate ceramic material, reduces the energy consumption by 23 percent, improves the compactness of the material and reduces the grain size, and improves the energy storage density and the energy storage efficiency by 22.2 percent and 13.5 percent respectively. The invention is going toThe energy storage density of the obtained material is 2.2-5.3J/cm while the production energy consumption is low3And the energy storage efficiency is 42-80%. The pulse power source has very important application value.

Description

Yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material and preparation method thereof
Technical Field
The invention relates to the field of research and technical development of functional materials, in particular to an yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material and a preparation method thereof, and the yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material can be used as a dielectric energy storage material and can be used as a power supply of a pulse capacitor.
Background
Dielectric capacitors are widely used in many advanced pulse power electronic systems due to their high power density, ultra-fast charge and discharge capability, long storage life, robustness, and excellent thermal stability. Such as cardiac pacemakers, nuclear effect simulation, camera flash lamps, metal forming, hybrid electric vehicles, space flight aircraft power systems, laser weapons, electromagnetic launch cannons and the like.
With the development of pulse power devices toward miniaturization and light weight, the development of dielectric materials with high energy density is more urgent. In the field of research of high energy density materials, there are 4 main dielectric materials that are currently receiving attention, including linear dielectrics, Ferroelectrics (FE), Antiferroelectrics (AFE), and relaxor ferroelectrics; a material in which an antiferroelectric material has a unique double hysteresis loop resulting from the transition between an antiferroelectric phase and a ferroelectric phase induced by an electric field and whose dielectric constant increases with an increase in the electric field is considered to be preferable.
To date, at 40 foundOf the many antiferroelectric materials, most are perovskite lead-based compounds, such as (Pb, La) (Zr, Ti) O3And the like. Although the energy storage density of lead-based compounds is high, the use of lead causes environmental problems and harms human health, and all countries in the world have strict limitations on the use of lead-containing electronic devices, so that the search for lead-free high energy storage density materials is always the focus of scientific researchers. The high-performance energy storage material has the characteristics of high energy storage density, high energy storage efficiency, capability of working in a high electric field and the like. 2016 perovskite structure silver niobate (AgNbO)3AN) antiferroelectric ceramic is reported to have high energy storage performance (energy storage density of 1.6-2.1J/cm)3Energy storage efficiency is about 38%). The literature reports that the sintering temperature of the silver niobate ceramic is usually over one thousand degrees, the heat preservation time is long, and the sintering energy consumption is large. On the other hand, from the application point of view, the energy storage performance of AN also needs to be further improved; increasing the saturation polarization is AN important parameter for improving the AN performance. The performance of the material can be regulated and controlled through element doping, the energy storage density and the energy storage efficiency of AN are improved, and the application prospect of AN is greatly expanded.
Disclosure of Invention
The first purpose of the invention is to reduce the high-temperature sintering time of the silver niobate-based ceramic and reduce the energy consumption on the premise of not reducing the energy storage performance; the second purpose of the invention is to improve the energy storage density and the energy storage efficiency of the silver niobate ceramic material by doping.
The inventor finds that the energy storage performance is maintained and the energy consumption is obviously reduced by adopting three-step sintering of a low temperature zone, a medium temperature zone and a high temperature zone and combining different oxygen pressure processes.
The inventor finds that yttrium doped silver at the A site can obviously increase silver ion vacancy defects in the material due to the difference of ion valence states; the oxygen vacancy is increased by doping niobium at the B site with hafnium; and a defect dipole is formed by the cation vacancy and the oxygen vacancy, so that the saturation polarization strength of the material is remarkably improved.
Further research by the inventor shows that co-doping of yttrium and hafnium can convert M1(Ferro-electric phase) -M2The phase transition temperature of the (antiferroelectric) phase is reduced to below room temperature, and the stability of the antiferroelectric phase is improvedQualitatively, reducing the remanent polarization;
the research of the inventor also finds that the yttrium and hafnium co-doping inhibits the growth of crystal grains, improves the density of crystal boundaries, enhances the breakdown field strength and improves the energy storage performance of the material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a silver niobate-based antiferroelectric ceramic material has a chemical formula of Ag1- 3xYxNb1-xHfxO3X is more than or equal to 0 and less than or equal to 0.10, preferably more than or equal to 0.03 and less than or equal to 0.05, and has the characteristic of electric field induced antiferroelectric-ferroelectric phase transition.
In the method, a three-step sintering process is utilized, medium-temperature sintering is increased, high-temperature sintering time is shortened, and energy consumption is reduced; the polarization strength of the material is obviously enhanced through doping, and the energy storage performance is improved;
the energy consumption reduction rate is calculated by comparing the total electricity consumption in the heat treatment process.
The total energy storage density and the effective energy storage density (hereinafter referred to as energy storage density) are calculated by the integration of the charging part and the discharging part of the P-E electric hysteresis loop relative to the Y axis respectively, and the energy loss can be calculated by the area surrounded by the electric hysteresis loop. The energy storage efficiency is the ratio of the energy storage density to the total energy storage density.
Preferably, the energy storage density of the yttrium and hafnium co-doped silver niobate antiferroelectric ceramic material is 5.3J/cm when x is 0.04 at room temperature3The energy storage efficiency was 78%.
Preferably, the saturation polarization strength of the yttrium and hafnium co-doped ceramic material is 43.5-52 μ C/cm at room temperature2。
Preferably, the energy storage density of the yttrium and hafnium co-doped silver niobate antiferroelectric ceramic material is 4.2-5.3J/cm at room temperature3And the energy storage efficiency is 69-80%.
The preparation method of the yttrium and hafnium co-doped silver niobate ceramic material comprises the following steps:
the method comprises the following steps: selecting Ag2O、Nb2O5、Y2O3、HfO2As starting material powder, according to the composition formula Ag1-3xYxNb1- xHfxO3Mixing materials, fully grinding to obtain powder A;
step two: calcining the A powder in oxygen atmosphere to obtain Ag1-3xYxNb1-xHfxO3Powder B;
step three: fully grinding the powder B, adding a proper amount of binder, granulating, and performing compression molding under a certain pressure to obtain a ceramic blank;
step four: the heat treatment process adopts a three-step sintering method, the obtained ceramic biscuit is subjected to gel discharge at low temperature in different oxygen gas pressures, and then is continuously sintered at medium temperature and high temperature to obtain the yttrium and hafnium co-doped silver niobate antiferroelectric ceramic material.
Preferably, the powder is ground by a ball grinding method in the step one, and the grinding time is 20 hours;
preferably, the temperature rise rate is 4-6 ℃/min during the powder sintering in the second step, the sintering temperature is 800-900 ℃, and the heat preservation time is 2-4 h;
preferably, the binder in the third step is polyvinyl alcohol, and the addition amount is 1-3 wt%.
Preferably, the grinding in the step three is completed in a ball mill, and the grinding time is 24 hours; the pressure of the tablet is 100-200 MPa; the size of the ceramic body is 1cm in diameter and 1mm in thickness.
Preferably, in the fourth step, the low-temperature sintering temperature is 500-600 ℃, the heating rate is 2-4 ℃/min, and the heat preservation time is 1-2 h;
preferably, in the fourth step, the temperature rising rate is 4-6 ℃/min from low temperature to medium temperature, the sintering temperature is 700-900 ℃, and the heat preservation time is 2-3 h; the temperature rise rate is 5-7 ℃/min from medium temperature to high temperature, the temperature is 1000-1100 ℃, and the heat preservation time is 1-2 h.
Preferably, the powder B is coated on the ceramic body in the sintering process to inhibit the decomposition of silver.
Preferably, the oxygen pressure in the furnace is maintained at 1atm during low-temperature sintering, 1 to 1.1atm during medium-temperature sintering, and 1.1 to 1.2atm during high-temperature sintering.
Compared with the prior art, the invention has the beneficial effects that: the process reduces the high-temperature sintering time of the silver niobate ceramic material, reduces the energy consumption by 23 percent, improves the compactness of the material and reduces the grain size, and improves the energy storage density and the energy storage efficiency by 22.2 percent and 13.5 percent respectively; the silver niobate-based antiferroelectric ceramic material is synthesized by doping yttrium and hafnium, so that the cation vacancy concentration and the oxygen vacancy concentration in the material are improved, the polarization strength is enhanced, the stability of an antiferroelectric phase is improved, and the growth of crystal grains is inhibited, thereby realizing high energy storage density and energy storage efficiency. The invention has good repeatability and simple process. According to the invention, the energy storage density of the obtained material is 2.2-5.3J/cm while the production energy consumption is reduced3And the energy storage efficiency is 42-80%. The pulse power source has very important application value.
Drawings
FIG. 1 is AN XRD diffractogram of AN-based ceramic materials prepared in comparative example 1 and examples 1-5 of the present invention;
FIG. 2 is a graph of the concentration of cationic vacancies as a function of doping level for ceramic materials prepared in accordance with examples 1-5 of the present invention;
FIG. 3 is a surface SEM image of a ceramic material prepared in comparative example 1 of the present invention;
FIG. 4 is a surface SEM image of a ceramic material prepared in example 1 of the present invention;
FIG. 5 is a surface SEM image of a ceramic material prepared in example 2 of the present invention;
FIG. 6 is a surface SEM image of a ceramic material prepared in example 3 of the present invention;
FIG. 7 is a surface SEM image of a ceramic material prepared in example 4 of the present invention;
FIG. 8 is a surface SEM image of a ceramic material prepared in example 5 of the present invention;
FIG. 9 is a graph showing the dielectric temperature spectrum and the dielectric frequency spectrum of the ceramic materials prepared in comparative example 1 and examples 1 to 5 according to the present invention, under the conditions of 1kHz, 10kHz, 100kHz, 1kHz, 10kHz, and 100kHz, in this order from top to bottom;
FIG. 10 is a P-E diagram of the ceramic materials prepared in comparative example 1 and examples 1-5 of the present invention;
FIG. 11 is a graph showing saturation polarization and remanent polarization of ceramic materials prepared in comparative example 1 and examples 1 to 5 according to the present invention;
fig. 12 is a graph showing the energy storage density and energy storage efficiency of the AN-based ceramic materials prepared in comparative example 1 and examples 1 to 5 according to the present invention.
Detailed Description
The following further details embodiments of the invention:
a silver niobate-based antiferroelectric ceramic material has a chemical formula of Ag1- 3xYxNb1-xHfxO3X is more than or equal to 0 and less than or equal to 0.10, preferably more than or equal to 0.03 and less than or equal to 0.05, and has the characteristic of electric field induced antiferroelectric-ferroelectric phase transition.
According to the method, yttrium and hafnium are codoped and combined with a three-step sintering method, so that the production energy consumption is reduced, the polarization strength of the silver niobate-based antiferroelectric ceramic material and the stability of an antiferroelectric phase are improved, the residual polarization strength is reduced, and the breakdown field strength is enhanced, so that the energy storage density and the energy storage efficiency of the material are improved. The energy density of the silver niobate-based antiferroelectric ceramic material is 2.2-5.3J/cm by adjusting the doping content of yttrium and hafnium to be more than or equal to 0 and less than or equal to 0.10 and x3And the energy storage efficiency is between 42 and 80 percent.
The preparation method of the yttrium and hafnium co-doped silver niobate antiferroelectric ceramic material comprises the following steps:
the method comprises the following steps: selecting Ag2O、Nb2O5、Y2O3、HfO2As starting material powder, according to the composition formula Ag1-3xYxNb1- xHfxO3Mixing materials, mixing, and grinding for 20 hours by a ball milling method to obtain powder A;
step two: sintering the powder A in an oxygen atmosphere at a heating rate of 4-6 ℃/min and a temperature of 800-900 ℃ for 2-4 h to obtain Ag1-3xYxNb1-xHfxO3Powder B;
step three: grinding the powder B for 24 hours by a ball milling method, then adding a proper amount of binder, wherein the addition amount of polyvinyl alcohol is 1-3 wt%, granulating, and pressing into a ceramic blank with the diameter of 1cm and the thickness of 1mm under the pressure of 100-200 MPa;
step four: putting the ceramic blank into an alumina crucible, covering a proper amount of powder B to prevent the silver oxide from being decomposed at high temperature, wherein the heat treatment process adopts a three-step sintering method, and the obtained ceramic blank is subjected to heat preservation for 2-3 hours at 500-600 ℃ at the temperature of 2-4 ℃/min in the oxygen atmosphere of 1 atm; and then heating to 700-900 ℃ at a heating rate of 4-6 ℃/min, keeping the temperature for 2-3 h in an oxygen atmosphere of 1-1.1 atm, and finally heating to 1000-1150 ℃ at a heating rate of 5-7 ℃, keeping the temperature for 1-2 h in an oxygen atmosphere of 1.1-1.2 atm to obtain the silver niobate-based antiferroelectric ceramic material.
Step five: and (3) polishing the obtained silver niobate-based antiferroelectric ceramic to 0.2-0.3 mm, coating a silver electrode with the diameter of 3-4 mm on the surface, sintering at 550 ℃ for 30min, and using the silver niobate-based antiferroelectric ceramic as an electrical property test.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Comparative example 1
The silver niobate-based ceramic material comprises the following components: AgNbO3(AgNbO3，x＝0)
(1) Calculating the mass of each component in the powder raw material according to the chemical formula, preparing according to the composition proportion, and taking Ag2O(2.31740g)、Nb2O5(2.65810g), the mixture was mixed by wet ball milling for 20 hours to mix the components uniformly to obtain powder A.
(2) Sintering the powder A in an oxygen atmosphere at the temperature of 800-900 ℃ to obtain powder B;
(3) fully grinding the powder B, then adding 1-3 wt% of binder polyvinyl alcohol, granulating, and pressing into a ceramic blank with the diameter of 1cm and the thickness of 1mm under the pressure of 100-200 MPa;
(4) putting the ceramic blank into an alumina crucible, covering a proper amount of powder B to prevent the silver oxide from being decomposed at high temperature, heating the obtained ceramic blank to 500-600 ℃ at a heating rate of 2-4 ℃/min in an oxygen atmosphere of 1atm, and preserving the temperature for 2-3 h; then continuously raising the temperature to 1000-1150 ℃ at the same speed, and preserving the temperature for 6h to obtain the silver niobate antiferroelectric ceramic material.
(5) XRD (X-ray diffraction) test is carried out on the silver niobate-based antiferroelectric ceramic obtained in the comparative example 1, and the test result is shown in figure 1;
(6) performing surface SEM test on the silver niobate-based antiferroelectric ceramic obtained in the comparative example 1 to obtain a surface appearance as shown in FIG. 3;
(7) the obtained silver niobate antiferroelectric ceramic is ground and polished to 0.25mm, a silver electrode with the diameter of 3mm is coated on the surface of the silver niobate antiferroelectric ceramic, and the silver electrode is sintered for 30min at 550 ℃ and used for electrical property test.
(8) The ceramic sample obtained in the comparative example 1 is subjected to the tests of dielectric temperature spectrum and dielectric frequency spectrum, and the test result is shown in figure 9;
(9) P-E of the ceramic material prepared in comparative example 1 is shown in FIG. 10;
(10) the results of calculation of the saturation polarization, remanent polarization and energy storage properties of the ceramic material obtained in comparative example 1 are shown in FIGS. 11 to 12. The saturation polarization of the obtained ceramic sample was 36.2. mu.C/cm2Residual polarization intensity of 3 μ C/cm2. The energy storage density of the obtained ceramic material is 1.8J/cm3The energy storage efficiency is 37%.
Example 1
The silver niobate-based ceramic material comprises the following components: AgNbO3(AgNbO3，x＝0)
(1) Calculating the mass of each component in the powder raw material according to the chemical formula, preparing according to the composition proportion, and taking Ag2O(2.31740g)、Nb2O5(2.65810g), and mixing for 20h by wet ball milling to mix the components uniformly to obtain powder A.
(2) Sintering the powder A in an oxygen atmosphere at the temperature of 800-900 ℃ to obtain powder B;
(3) fully grinding the powder B, then adding 1-3 wt% of binder polyvinyl alcohol, granulating, and pressing into a ceramic blank with the diameter of 1cm and the thickness of 1mm under the pressure of 100-200 MPa;
(4) putting the ceramic blank into an alumina crucible, covering a proper amount of powder B to prevent the silver oxide from being decomposed at high temperature, wherein the heat treatment process adopts a three-step sintering method, and the obtained ceramic blank is heated to 500-600 ℃ in an oxygen atmosphere of 1atm at the heating rate of 2-4 ℃/min and is kept for 1-2 h; and then continuously heating to 700-900 ℃ at the heating rate of 4-6 ℃/min, preserving heat for 2-3 h in the oxygen atmosphere of 1-1.1 atm, then heating to 1000-1150 ℃ at the heating rate of 5-7 ℃, preserving heat for 1-2 h in the oxygen atmosphere of 1.1-1.2 atm, and obtaining the silver niobate antiferroelectric ceramic material.
(5) The silver niobate-based antiferroelectric ceramic obtained in the example 1 is subjected to XRD test, and the test result is shown in figure 1;
(6) positron annihilation testing is carried out on the defect characteristics of the embodiment, and the testing result is shown in fig. 2;
(7) the silver niobate-based antiferroelectric ceramic obtained in the embodiment 1 is subjected to surface SEM test, and the obtained surface appearance is shown in FIG. 4;
(8) the obtained silver niobate antiferroelectric ceramic is ground and polished to 0.25mm, a silver electrode with the diameter of 3mm is coated on the surface of the silver niobate antiferroelectric ceramic, and the silver electrode is sintered for 30min at 550 ℃ and used for electrical property test.
(9) The ceramic sample obtained in the example 1 was subjected to the dielectric temperature spectrum and dielectric frequency spectrum test, and the test results are shown in fig. 9;
(10) P-E of the ceramic material prepared in this example is shown in FIG. 10;
(11) the results of calculation of the saturation polarization, the remanent polarization and the energy storage performance of the ceramic material obtained in example 1 are shown in FIGS. 11 to 12. The saturation polarization of the obtained ceramic sample was 38.1. mu.C/cm2Residual polarization intensity of 2.8. mu.C/cm2. The energy storage density of the obtained ceramic material is 2.2J/cm3The energy storage efficiency is 42%. Compared with comparative example 1, the process reducesThe high-temperature sintering time of the silver niobate ceramic material is shortened by 23 percent, and the energy storage density and the energy storage efficiency are respectively improved by 22.2 percent and 13.5 percent;
example 2
The silver niobate-based ceramic material comprises the following components: ag0.91Y0.03Nb0.97Hf0.03O3(Ag1-3xYxNb1-xHfxO3，x＝0.03)
(1) Calculating the mass of each component in the powder raw material according to the chemical formula, preparing according to the composition proportion, and taking Ag2O(2.10883g)、Y2O3(0.06774g)、Nb2O5(2.57836)、HfO2(0.12629g), the preparation process of example 1 was repeated;
(2) XRD testing was performed on this example, and the results are shown in FIG. 1;
(3) positron annihilation testing is carried out on the defect characteristics of the embodiment, and the testing result is shown in fig. 2;
(4) the surface SEM test was performed on the present example, and the obtained surface topography is as shown in fig. 5;
(5) the ceramic material obtained in the embodiment is tested for a dielectric temperature spectrum and a dielectric frequency spectrum, and the test result is shown in fig. 8;
(6) P-E of the ceramic material prepared in this example is shown in FIG. 10;
(7) the results of calculation of the saturation polarization, the remanent polarization and the energy storage performance of the ceramic material obtained in this example are shown in FIGS. 11 to 12. The saturation polarization of the obtained ceramic sample was 43.5. mu.C/cm2Residual polarization intensity of 2.1. mu.C/cm2. The energy storage density of the obtained ceramic material is 4.2J/cm3The energy storage efficiency was 69%.
Example 3
The silver niobate-based ceramic material comprises the following components: ag0.88Y0.04Nb0.96Hf0.04O3(Ag1-3xYxNb1-xHfxO3，x＝0.04)
(1) Calculating the mass of each component in the powder raw material according to the chemical formula, preparing according to the composition proportion, and taking Ag2O(2.03931g)、Y2O3(0.09032g)、Nb2O5(2.55178)、HfO2(0.16839g), the preparation process of example 1 was repeated;
(2) XRD testing was performed on this example, and the results are shown in FIG. 1;
(3) positron annihilation testing is carried out on the defect characteristics of the embodiment, and the testing result is shown in fig. 2;
(4) the surface SEM test was performed on the present example, and the obtained surface topography is as shown in fig. 6;
(5) the ceramic material obtained in the embodiment is subjected to a dielectric temperature spectrum and a dielectric frequency spectrum test, and the test result is shown in fig. 9;
(6) P-E of the ceramic material prepared in this example is shown in FIG. 10;
(7) the results of calculation of the saturation polarization, the remanent polarization and the energy storage performance of the ceramic material obtained in this example are shown in FIGS. 11 to 12. The saturation polarization of the obtained ceramic sample was 52. mu.C/cm2Residual polarization intensity of 1 μ C/cm2. The energy storage density of the obtained ceramic material is 5.3J/cm3The energy storage efficiency was 78%.
Example 4
The silver niobate-based ceramic material comprises the following components: ag0.85Y0.05Nb0.95Hf0.05O3(Ag1-3xYxNb1-xHfxO3，x＝0.05)
(1) Calculating the mass of each component in the powder raw material according to the chemical formula, preparing according to the composition proportion, and taking Ag2O(1.96979g)、Y2O3(0.11291g)、Nb2O5(2.52520)、HfO2(0.21049g), the preparation process of example 1 was repeated;
(2) XRD testing was performed on this example, and the results are shown in FIG. 1;
(3) positron annihilation testing is carried out on the defect characteristics of the embodiment, and the testing result is shown in fig. 2;
(4) the surface SEM test was performed on this example, and the obtained surface topography was as shown in fig. 7;
(5) the ceramic material obtained in the embodiment is subjected to a dielectric temperature spectrum and a dielectric frequency spectrum test, and the test result is shown in fig. 9;
(6) P-E of the ceramic material prepared in this example is shown in FIG. 10;
(7) the results of calculation of the saturation polarization, the remanent polarization and the energy storage performance of the ceramic material obtained in this example are shown in FIGS. 11 to 12. The saturation polarization of the obtained ceramic sample was 44.7. mu.C/cm2Residual polarization intensity of 1.2. mu.C/cm2. The energy storage density of the obtained ceramic material is 4.7J/cm3The energy storage efficiency is 80%.
Example 5
The silver niobate-based ceramic material comprises the following components: ag0.7Y0.1Nb0.9Hf0.1O3(Ag1-3xYxNb1-xHfxO3，x＝0.10)
(1) Calculating the mass of each component in the powder raw material according to the chemical formula, preparing according to the composition proportion, and taking Ag2O(1.62218g)、Y2O3(0.22581g)、Nb2O5(2.39229)、HfO2(0.42098g), the preparation process of example 1 was repeated;
(2) XRD testing was performed on this example, and the results are shown in FIG. 1;
(3) positron annihilation testing is carried out on the defect characteristics of the embodiment, and the testing result is shown in fig. 2;
(4) the surface SEM test was performed on the present example, and the obtained surface topography is as shown in fig. 8;
(5) the ceramic material obtained in the embodiment is subjected to a dielectric temperature spectrum and a dielectric frequency spectrum test, and the test result is shown in fig. 9;
(6) P-E of the ceramic material prepared in this example is shown in FIG. 10;
(7) the results of calculation of the saturation polarization, the remanent polarization and the energy storage performance of the ceramic material obtained in this example are shown in FIGS. 11 to 12. The saturation polarization of the obtained ceramic sample was 31.9. mu.C/cm2Residual polarization intensity of 2.6. mu.C/cm2. The energy storage density of the obtained ceramic material is 3.7J/cm3The energy storage efficiency is 64%.
As can be seen from FIG. 1, comparative example 1 and example 1-5, the prepared undoped and yttrium and hafnium co-doped silver niobate ceramic materials are all in a single perovskite structure, and no second phase is generated; as can be seen from the (220) peak and the (008) peak cleaved at around 46 °, as the content of yttrium and hafnium increases, the diffraction peak of XRD shifts to a high angle due to the smaller unit cell volume caused by the substitution of small radius yttrium ions for large radius Ag ions; in addition, the two peaks approach as the doping amount increases, which means that M is1In the ferroelectrics phase M2The transition of the antiferroelectric phase and the surface doping improve the stability of the antiferroelectric phase.
From fig. 7, it can be seen that co-doping of yttrium and hafnium significantly increases the defect concentration in the material, the defect dipole generated by the defect will significantly increase the saturation polarization of the material, and from examples 2 to 4, the increase of the saturation polarization can be significantly seen, thereby significantly improving the energy storage performance.
As can be seen from fig. 2 to 6, the energy storage ceramic materials of comparative example 1 and examples 1 to 5 have denser surface morphology, and the grain size gradually decreases with the increase of the doping amount; the reduction of the grain size will increase the breakdown field strength and improve the energy storage performance.
The results of the phase transition temperature test of the silver niobate-based ceramic materials of examples 1 to 5 are shown in FIG. 8, and it can be seen that co-doping of yttrium and hafnium makes the ferroelectric phase (M)1) An inhibited, ferrielectric phase (M) is obtained1) When the temperature is reduced to below room temperature, the antiferroelectric phase region is enlarged, which shows that the antiferroelectric property of the material is enhanced along with the increase of doping amount of yttrium and hafnium, thus being beneficial to improving the energy storage performance;
results of the hysteresis loop diagram, the polarization intensity diagram and the energy storage performance of the silver niobate-based ceramic materials of comparative example 1 and examples 1 to 5 are shown in fig. 9 to 11, and the hysteresis loop becomes more narrow and the W becomes more inclined as the doping increases, and W is calculatedrecAnd η both increase gradually. When the doping amount x of yttrium and hafnium is 0.04, the maximum polarization intensity reaches 52 mu C/cm2Energy storage density WrecUp to 5.3J/cm3The energy storage efficiency reaches 78 percent and is far higher than the energy storage performance (W) of pure silver niobaterec＝2.2J/cm3，η＝42％)。
In conclusion, the energy consumption for preparing the silver niobate ceramic material can be reduced and the energy storage performance of the silver niobate ceramic material can be obviously improved by co-doping yttrium and hafnium and combining a three-step solid-phase sintering method.

Claims (9)

1. An yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material is characterized in that: the chemical general formula of the silver niobate-based antiferroelectric ceramic material is Ag x1-3Y x Nb x1-Hf x O3，0≤x≤0.10。
2. The yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material according to claim 1, wherein: the chemical formula of the silver niobate-based antiferroelectric ceramic material is Ag x1-3Y x Nb x1-Hf x O3，0.03≤x≤0.05。
3. The method for preparing an yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material according to claim 1 or 2, wherein:
(1) selecting Ag2O、Nb2O5、Y2O3、HfO2As starting material powder, according to the composition formula Ag x1-3Y x Nb x1-Hf x O3Mixing materials, fully grinding to obtain powder A;
(2) sintering the A powder in an oxygen atmosphere at 800-900 ℃ to obtain Ag x1-3Y x Nb x1-Hf x O3Powder B;
(3) fully grinding the powder B, adding a binder, granulating, and performing compression molding under a certain pressure to obtain a ceramic blank;
(4) and (3) performing gel discharge on the ceramic blank at low temperature under different oxygen gas pressures by adopting a three-step sintering method, and then continuously sintering at medium temperature and high temperature to obtain the yttrium and hafnium co-doped silver niobate antiferroelectric ceramic material.
4. The yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material according to claim 1 or 2, wherein: and (2) grinding the powder in the step (1) by a ball grinding method for 18-24 h.
5. The method for preparing a silver niobate-based antiferroelectric ceramic material according to claim 1 or 2, wherein: the sintering conditions in the step (2) are that the heating rate is 4-6 ℃/min, the sintering temperature is 800-900 ℃, and the heat preservation time is 2-4 h.
6. The yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material according to claim 1 or 2, wherein: the binder in the step (3) is polyvinyl alcohol, and the addition amount of the polyvinyl alcohol is 1-3 wt% based on the mass of the powder B.
7. The yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material according to claim 1 or 2, wherein: the grinding in the step (3) is finished in a ball mill, and the grinding time is 18-24 h; the pressure of the tablet is 100-200 MPa; the ceramic blank has a diameter of 1-1.1 cm and a thickness of 0.9-1.1 mm.
8. The yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material according to claim 1 or 2, wherein: in the step (4), the low-temperature sintering temperature is 500-600 ℃, the heating rate is 2-4 ℃/min, and the heat preservation time is 1-2 h; the temperature rise rate is 4-6 ℃/min during medium-temperature sintering, the heat preservation time is 2-3 h when the sintering temperature is 700-900 ℃, the temperature rise rate is 5-7 ℃/min during high-temperature sintering, the temperature is 1000-1100 ℃, and the heat preservation time is 1-2 h.
9. The yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material according to claim 1 or 2, wherein: in the step (4), the oxygen pressure in the furnace is maintained at 1atm during low-temperature sintering, the oxygen pressure in the furnace is maintained at 1-1.1 atm during medium-temperature sintering, and the oxygen pressure in the furnace is maintained at 1.1-1.2 atm during high-temperature sintering.
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