CN116425536A - Ti-doped barium strontium gadolinium niobate ferroelectric ceramic material with non-axiom modulation structure and preparation method thereof - Google Patents
Ti-doped barium strontium gadolinium niobate ferroelectric ceramic material with non-axiom modulation structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Ti-doped strontium barium gadolinium niobate ferroelectric ceramic material with a non-axiom modulation structure, the structural formula of which is Sr 0.485 Ba 0.47 Gd 0.03 Nb 2‑x Ti x O 6‑δ The value of x is 0.01-0.2. The preparation method comprises the following steps: baCO is carried out 3 、SrCO 3 、Gd 2 O 3 、Nb 2 O 5 、TiO 2 Mixing, ball milling, drying and presintering to obtain presintering powder; granulating the presintered powder, holding the presintered powder under cold isostatic pressing, discharging glue, burying, and sintering under gas atmosphere. By adding a catalyst to Sr 0.485 Ba 0.47 Gd 0.03 Nb 2 O 6 The system is doped with variable valence Ti, so that the ceramic material has a room temperature non-axiom modulation structure and excellent dielectric propertyThe slender electric hysteresis loop obtains good room-temperature energy storage performance and excellent temperature stability, and realizes wide-temperature-range high-energy storage performance in the same dielectric material.
Description
Technical Field
The invention belongs to the technical field of ceramic material preparation, and particularly relates to a Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material with a non-axiality modulation structure, and a preparation method of the Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material.
Background
Dielectric ceramic capacitor as a physical energy storage device, since it has extremely high power density (10 4 ～10 8 W/kg) and is widely used in pulse power devices. However, compared to other electrical energy storage and conversion materials (e.g., electrochemical capacitors, fuel cells), the dielectric energy storage density is low, and in many applications, a capacitor with a heavy volume needs to be built to obtain sufficient capacitance, which severely limits the miniaturization and integration of the device.
Barium strontium niobate (Sr, ba, gd) Nb with tungsten bronze structure 2 O 6 Of NbO as material 6 The octahedron is used as a basic structural unit, and the filling condition of the non-equivalent crystallographic gap position is adjusted to enable the octahedron to generate various ferroelectric and relaxor ferroelectric materials with different phase transition temperatures and diffusion degrees, so that the octahedron is a key material for researching and developing a lead-free electrostatic capacitor. However, the high energy storage characteristic at room temperature and the excellent temperature stability in polycrystalline ceramics are extremely difficult to achieve simultaneously in the same dielectric material. Thus, a room-temperature non-axiom modulation structure is built in the inorganic ferroelectric relaxor to further promote the unfilled tungsten bronze structure (Sr, ba, gd) Nb 2 O 6 Is a battery of the battery. Introducing a non-axiom modulation structure into a tungsten bronze structure niobate relaxor so as to obtain high energy storage density and energy storage efficiency at room temperature; and simultaneously, the applicable temperature range of the energy storage characteristic is widened, so that the current technical bottleneck is further broken through, and the high-efficiency dielectric energy storage material suitable for large-scale production and industrialized application is created.
Disclosure of Invention
The invention aims to provide a Ti-doped strontium barium gadolinium niobate ferroelectric ceramic material with a room temperature non-axiom modulation structure, which has a room temperature non-axiom modulation structure and excellent dielectric properties.
The invention also aims to provide a preparation method of the Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material.
The technical proposal adopted by the invention is that the Ti-doped strontium barium gadolinium niobate ferroelectric ceramic material with a non-axiom modulation structure has the structural formula of Sr 0.485 Ba 0.47 Gd 0.03 Nb 2-x Ti x O 6-δ Wherein, the value of x is 0.01-0.2, and preferably, the value of x is 0.08.
The invention adopts another technical scheme that the Ti-doped barium strontium niobate ferroelectric ceramic material with a non-axiom modulation structure is obtained by inert atmosphere sintering, which comprises the following steps:
step 1, according to Sr 0.485 Ba 0.47 Gd 0.03 Nb 2-x Ti x O 6-δ Respectively weighing BaCO with the purity of more than 99.00 percent 3 、SrCO 3 、Gd 2 O 3 、Nb 2 O 5 、TiO 2 Fully mixing, ball milling and drying to obtain a raw material mixture;
and 3, granulating the presintered powder under the action of a polyvinyl alcohol binder, keeping the presintered powder in a tabletting mode under cold isostatic pressing, discharging glue, burying the presintered powder, and sintering the buried presintered powder in a gas atmosphere to obtain the Ti-doped strontium barium gadolinium niobate ferroelectric ceramic material.
The present invention is also characterized in that,
in the step 2, the presintering temperature is 1000-1150 ℃ and the presintering time is 3-6 hours.
In the step 3, the sintering temperature is 1280-1340 ℃ and the sintering time is 2-6 hours.
In the step 3, the gas atmosphere is air, nitrogen or oxygen.
The beneficial effects of the invention are as follows: by adding a catalyst to Sr 0.485 Ba 0.47 Gd 0.03 Nb 2 O 6 Adding variable valence Ti into the system to make the alloyThe obtained ceramic material has a room temperature non-metric modulation structure, excellent dielectric property and slender electric hysteresis loop, good room temperature energy storage property and excellent temperature stability property are obtained, and the wide temperature range high energy storage property is realized in the same dielectric material.
Drawings
FIG. 1 is a scanning electron microscope microscopic morphology of the ceramic surface prepared in comparative example 1 and examples 1-3;
FIG. 2 is a graph of dielectric constant and dielectric loss as a function of temperature for the ceramic material prepared in example 2 at different test frequencies;
FIG. 3 is an XRD pattern for the ceramic materials prepared in comparative example 1 and examples 2, 4, and 5;
FIG. 4 is a composite impedance spectrum at 500℃for the ceramic materials prepared in comparative example 1 and examples 1 to 3;
FIG. 5 is a plot of selected area electron diffraction patterns with axes of [110] at room temperature for the ceramic material prepared in example 4, illustrating the modulated wave vector.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The Ti-doped strontium barium gadolinium niobate ferroelectric ceramic material with the non-axiom modulation structure has the structural formula of Sr 0.485 Ba 0.47 Gd 0.03 Nb 2-x Ti x O 6-δ Wherein, the value of x is 0.01-0.2; preferably, x has a value of 0.08. The ceramic material is of a non-filled tungsten bronze structure.
In the invention, oxygen vacancies of the tungsten bronze structure ferroelectric material are regulated and controlled by B-site variable valence Ti ion doping combined with inert atmosphere sintering technology, and a polarization unit BO is induced 6 The octahedron distortion builds a non-axiality modulation structure.
The invention relates to a preparation method of Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material with a non-axiom modulation structure, which specifically comprises the following steps:
step 1, according to Sr 0.485 Ba 0.47 Gd 0.03 Nb 2-x Ti x O 6-δ Respectively weighing BaCO with the purity of more than 99.00 percent 3 、SrCO 3 、Gd 2 O 3 、Nb 2 O 5 、TiO 2 Fully mixing and ball milling for 16-24 hours, and drying for 12-24 hours at the temperature of 80-100 ℃ to obtain a raw material mixture;
preferably, the raw material mixture is presintered for 4 hours at 1100 ℃;
step 3, granulating the presintered powder under the action of a polyvinyl alcohol (PVA) binder, keeping the presintered powder for 1min under 200MPa cold isostatic pressing, then heating to 600 ℃ at 1 ℃/min for discharging glue, and sintering the presintered powder in a gas atmosphere for 2-6 hours under the condition of 1280-1340 ℃ to obtain the Ti-doped tungsten bronze structure ferroelectric energy storage ceramic material;
the gas atmosphere is air, nitrogen or oxygen;
preferably, the sintering temperature is 1320 ℃ and the sintering time is 2 hours under nitrogen atmosphere.
The invention dopes Sr by changing the valence Ti 0.485 Ba 0.47 Gd 0.03 Nb 2 O 6 The ceramic system inhibits abnormal growth of anisometric grains of the tungsten bronze structure ceramic, so that a compact ferroelectric energy storage material is formed, and energy dissipation under an electric field is reduced; in addition, after the ceramic is annealed in inert atmosphere, the Ti at the B position has obvious valence variation and is prepared by the following steps of 4+ To Ti (Ti) 3+ Ti and 2+ oxygen vacancies in the ceramic are induced, so that the ceramic presents a non-metric modulation structure after being higher than the Curie temperature, and the temperature stability of the ceramic capacitor is remarkably widened; the composition does not relate to Bi, na, K and other elements which are easy to volatilize in the high-temperature sintering process, is easy to integrate devices, is simple to operate, has low requirements on equipment, manpower and sites, and is expected to realize industrial production.
Example 1
The invention relates to a preparation method of Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material with a non-axiom modulation structure, which specifically comprises the following steps:
step 1, according to Sr 0.485 Ba 0.47 Gd 0.03 Nb 1.95 Ti 0.05 O 6-δ Respectively weighing SrCO with the purity of 99.00 percent 3 2.4989g BaCO with a purity of 99.00% 3 3.2112g of Gd with purity of 99.99% 2 O 3 0.1879g of Nb with purity of 99.90 percent 2 O 5 8.9634g of TiO with purity of 99.85% 2 0.1386g, putting into a nylon pot, using zirconium balls as grinding balls and absolute ethyl alcohol as ball milling media, ball milling for 16 hours with a ball mill at 400 rpm, drying for 15 hours at 80 ℃ in a drying oven, grinding for 30 minutes with a mortar, and sieving with a 80-mesh sieve to obtain a raw material mixture;
and 3, adding a polyvinyl alcohol aqueous solution with the mass fraction of 5% (the mass of the polyvinyl alcohol aqueous solution is 50% of the mass of the presintered powder) into the presintered powder, granulating, sieving with a 100-mesh sieve to prepare spherical particles, putting the spherical particles into a stainless steel die with the diameter of 15mm, pressing the spherical particles into a cylindrical blank with the thickness of 1.5mm under the pressure of 200MPa by using cold isostatic pressing, putting the cylindrical blank on a zirconia flat plate, putting the zirconia flat plate into an alumina closed sagger, heating to 500 ℃ at the heating rate of 1 ℃/min, preserving heat for 2 hours for discharging glue, cooling to room temperature, lifting the obtained green blank by presintered powder by presintered, heating to 1000 ℃ in a tube furnace at the heating rate of 5 ℃/min, continuously heating to 1320 ℃ at the heating rate of 3 ℃/min, sintering for 2 hours under the Air atmosphere, and naturally cooling to room temperature along with the furnace to obtain the Ti-doped strontium barium gadolinium ferroelectricity energy storage ceramic material (Ti/SBNG-0.05-Air).
Example 2
The invention relates to a preparation method of Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material with a non-axiom modulation structure,
in step 1 of the present embodiment, the following Sr is used 0.485 Ba 0.47 Gd 0.03 Nb 1.92 Ti 0.08 O 6-δ Respectively weighing SrCO with the purity of 99.00 percent 3 2.5080g BaCO with a purity of 99.00% 3 3.2230g of Gd with purity of 99.99% 2 O 3 0.1886g of Nb with purity of 99.90% 2 O 5 8.8579g of TiO with purity of 99.85% 2 0.2226g, the other steps are the same as in example 1, and a Ti-doped strontium barium gadolinium niobate ferroelectric energy storage ceramic material (Ti/SBNG-0.08-Air) is obtained.
Example 3
The invention relates to a preparation method of Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material with a non-axiom modulation structure, which specifically comprises the following steps:
in step 1 of this embodiment, the following is performed according to Sr 0.485 Ba 0.47 Gd 0.03 Nb 1.88 Ti 0.12 O 6-δ Respectively weighing SrCO with the purity of 99.00 percent 3 2.5203g BaCO with a purity of 99.00% 3 3.2388g of Gd with purity of 99.99% 2 O 3 0.1895g of Nb with purity of 99.90% 2 O 5 8.7159g of TiO with purity of 99.85% 2 0.3355g, the other steps are the same as in example 1, and a Ti-doped strontium barium gadolinium niobate ferroelectric energy storage ceramic material (Ti/SBNG-0.12-Air) is obtained.
Example 4
The invention relates to a preparation method of Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material with a non-axiom modulation structure, which specifically comprises the following steps:
in step 1 of the present embodiment, the following Sr is used 0.485 Ba 0.47 Gd 0.03 Nb 1.92 Ti 0.08 O 6-δ Respectively weighing SrCO with the purity of 99.00 percent 3 2.5080g BaCO with a purity of 99.00% 3 3.2230g of Gd with purity of 99.99% 2 O 3 0.1886g of Nb with purity of 99.90% 2 O 5 8.8579g of TiO with purity of 99.85% 2 0.2226g, the sintering atmosphere was changed from the air in step 3 of example 1 to a nitrogen atmosphere, and the other steps were the same as in example 1 to obtain N 2 Atmosphere sintered Ti-doped barium strontium gadolinium niobate ferroelectric energy storage ceramic material (Ti/SBNG-0.08-N) 2 )。
Example 5
The invention relates to a preparation method of Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material with a non-axiom modulation structure, which specifically comprises the following steps:
in step 1 of the present embodiment, the following Sr is used 0.485 Ba 0.47 Gd 0.03 Nb 1.92 Ti 0.08 O 6 Respectively weighing SrCO with the purity of 99.00 percent 3 2.5080g BaCO with a purity of 99.00% 3 3.2230g of Gd with purity of 99.99% 2 O 3 0.1886g of Nb with purity of 99.90% 2 O 5 8.8579g of TiO with purity of 99.85% 2 0.2226g, the sintering atmosphere was changed from the air in step 3 of example 1 to an oxygen atmosphere, and the other steps were the same as in example 1 to obtain O 2 Atmosphere sintered Ti-doped barium strontium gadolinium niobate ferroelectric energy storage ceramic material (Ti/SBNG-0.08-O) 2 )。
Comparative example 1
According to Sr 0.485 Ba 0.47 Gd 0.03 Nb 2 O 6 Respectively weighing SrCO with the purity of 99.00 percent 3 2.4795g BaCO with a purity of 99.00% 3 3.2119g of Gd with purity of 99.99% 2 O 3 0.1864g of Nb with purity of 99.90% 2 O 5 9.1221g, the other steps were the same as in example 1, to obtain a Gd-doped SBN tungsten bronze structure ferroelectric energy storage ceramic material (SBN-Gd 0.03).
The ceramic materials prepared in the comparative example 1 and the examples 1 to 3 are subjected to microscopic morphology test by adopting Carle Zeiss GeminiSEM field emission scanning electron microscope, and as can be seen from fig. 1, the introduction of valence Ti promotes the evolution of rod-shaped grains into equiaxed grains, which is beneficial to densification of the ceramic and reduction of dielectric loss of the energy storage material;
FIG. 3 is an XRD pattern for the ceramic materials prepared in comparative example 1 and examples 2, 4, and 5; from the figure it can be concluded that pure phases of the tungsten bronze structure are obtained, however, due to the different sintering atmospheres, originating from the polarization unit BO 6 The symmetry of its tetragonal phase changes, especially at N 2 In the atmosphere, the oxygen defect concentration is high, and the structural distortion is serious.
And (3) polishing the surface of the prepared ceramic material with 320-800-1500-mesh sand paper to a thickness of 0.5-0.6 mm, coating silver paste with a thickness of 0.01-0.03 mm on the upper and lower surfaces of the ceramic material, and placing the ceramic material in a resistance furnace for heat preservation at 840 ℃ for 30 minutes. As can be seen from FIG. 2, the dielectric properties of the energy storage dielectric ceramic material of example 2 are tested by adopting Agilent,4980ALCR meter, and the dielectric constants of the energy storage dielectric ceramic material at different temperatures show wider spectral peaks in the frequency range of 1 kHz-2 MHz, and the maximum dielectric constant gradually decreases along with the increase of the test frequency, and the temperature corresponding to the spectral peaks moves to the high temperature direction, so that the significantly enhanced relaxation property of the ceramic material is shown, and the elongated electric hysteresis loop is facilitated to be obtained. Ceramic electrical performance tests were performed using a HIOKI3532-50 and Agilent 4980A precision impedance analyzer, the results of which are shown in FIG. 4; the doping of the variable valence Ti induces the reduction of the symmetry of the tetragonal phase structure by combining the XRD test of a D/max-2200X-ray diffractometer and the electron diffraction test of a selected area of a high-resolution transmission electron microscope TEM, and the characteristic of a non-axiality modulation structure is presented at the room temperature higher than the Curie temperature. According to the invention, variable-valence Ti is introduced into the ceramic material, so that the relaxation of the ceramic is obviously enhanced, and when the value of x is 0.08, the maximum dielectric constant of the material is 1407.443, and the dielectric constant of the material at room temperature is 1301.65.
FIG. 5 is a plot of selected area electron diffraction patterns with axes of [110] at room temperature for the ceramic material prepared in example 4, illustrating the modulated wave vector. From the figure, it can be seen that the ceramic material obtained by sintering under nitrogen atmosphere has a non-metric modulation structure at room temperature.
In the invention, oxygen vacancy of the ferroelectric material with the tungsten bronze structure is regulated and controlled by combining B-site variable valence ion doping with inert atmosphere sintering technology, and a polarization unit BO is induced 6 On one hand, the intrinsic high dielectric constant, relatively low sintering temperature of the relaxation body, low temperature change rate caused by 'dispersion phase change' and the ferroelectric property of 'fine' almost no hysteresis are easy to effectively maintain, and the room temperature high energy storage density and energy storage efficiency are obtained; on the other hand, the adjustable non-axiality period influences depolarization response, so that ferroelectric micro-domains still exist when paraelectric phase (polarization is obviously reduced) occurs, and the film is macroscopically thinThe long electric hysteresis loop obviously widens the applicable temperature range of the energy storage characteristic, has good application prospect and can meet the requirements of the pulse power industry.
Claims (6)
1. A Ti-doped strontium barium gadolinium niobate ferroelectric ceramic material with a non-axiom modulation structure is characterized in that the structural formula is Sr 0.485 Ba 0.47 Gd 0.03 Nb 2-x Ti x O 6-δ Wherein, the value of x is 0.01-0.2.
2. The Ti-doped barium strontium niobate ferroelectric ceramic material with a non-axiom modulation structure according to claim 1, wherein x has a value of 0.08.
3. The method for preparing the Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material with the non-axiom modulation structure according to claim 1, which is characterized by comprising the following steps:
step 1, according to Sr 0.485 Ba 0.47 Gd 0.03 Nb 2-x Ti x O 6-δ Respectively weighing BaCO with the purity of more than 99.00 percent 3 、SrCO 3 、Gd 2 O 3 、Nb 2 O 5 、TiO 2 Fully mixing, ball milling and drying to obtain a raw material mixture;
step 2, presintering the raw material mixture to obtain presintering powder;
and 3, granulating the presintered powder under the action of a polyvinyl alcohol binder, keeping the presintered powder in a tabletting mode under cold isostatic pressing, discharging glue, burying the presintered powder, and sintering the buried presintered powder in a gas atmosphere to obtain the Ti-doped strontium barium gadolinium niobate ferroelectric ceramic material.
4. The method for preparing a Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material with a non-axiom modulation structure according to claim 3, wherein in the step 2, the pre-sintering temperature is 1000-1150 ℃ and the pre-sintering time is 3-6 hours.
5. The method for preparing the Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material with the non-axiom modulation structure according to claim 3, wherein in the step 3, the sintering temperature is 1280-1340 ℃ and the sintering time is 2-6 hours.
6. The method for preparing a Ti-doped barium strontium niobate gadolinium ferroelectric ceramic material with a non-axiom modulation structure according to claim 3, wherein in the step 3, the gas atmosphere is air, nitrogen or oxygen.
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