CN114716248B - Rare earth doped tungsten bronze structure ceramic material with high energy storage property and preparation method thereof - Google Patents
Rare earth doped tungsten bronze structure ceramic material with high energy storage property and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a rare earth doped tungsten bronze structure ceramic material with high energy storage property, which has the structural formula (Sr) 0.53‑ 0.15x Ba 0.47 Gd x ) 1‑y RE y Nb 2 O 6 The value of x is 0-0.1, and the value of y is 0.01-0.08. The invention also discloses a preparation method of the BaCO composite material, which comprises the steps of 3 、SrCO 3 、Gd 2 O 3 、RE 2 O 3 、Nb 2 O 5 Mixing, ball milling, drying, presintering, granulating, tabletting, removing colloid, and sintering. Abnormal growth of anisometric grains of the tungsten bronze structure ceramic is restrained through the A-site rare earth doped ceramic system, a compact ferroelectric energy storage material is formed, relaxation characteristics are increased, energy dissipation under an electric field is reduced, in addition, elements such as Bi, na, K and the like which are easy to volatilize in a high-temperature sintering process are not involved in the ceramic composition, integration of devices is easy, and requirements on equipment, manpower and sites are low.
Description
Technical Field
The invention belongs to the technical field of ceramic material preparation, and particularly relates to a rare earth doped tungsten bronze structure ceramic material with high energy storage property and a preparation method of the ceramic material.
Background
In recent years, lead-free piezoelectrics have been increasingly attracting attention because of finding new functional characteristics in strain, electric cards, thermoelectric, photoelectric, luminescent and the like, in addition to research on improving the piezoelectrics performance in order to replace lead-containing materials. Dielectric ceramics as an advanced energy storage material, which has a high power density (up to 10 8 W/kg), high working voltage and quick charge and discharge speedAnd the working temperature range is wide, and the application is very wide in the aspects of hybrid electric vehicles, microwave communication, pulse power weapons, electromagnetic ejection, pulse power electronic devices and the like.
The tungsten bronze system is an important branch in a lead-free piezoelectric ferroelectric material system, and the composition general formula is (A1) 2 (A2) 4 C 4 (B1) 2 (B2) 8 O 30 Different metal cations selectively occupy 5 non-equivalent crystallographic gap positions of A1, A2, B1, B2 and C positions according to the radius and valence state, and flexible and changeable structural characteristics and functional characteristics can be induced by adjusting the filling condition of the crystallographic gap positions. But the research on the energy storage performance is mainly focused on Sr 2 NaNb 5 O 15 The volatilization of Na element in the high-temperature sintering process is unfavorable for obtaining compact ceramic, and the ceramic system not only has ferroelectric-paraelectric phase transition, but also has ferro-elastic phase transition, and the complex phase transition process leads to domain inversion and migration at high temperature to generate energy dissipation, reduce breakdown field intensity and limit the application of the ceramic system in energy storage; accordingly, in the face of the development of high integration and miniaturization of energy storage devices, there is an urgent need to seek and develop dielectric energy storage materials having high performance.
Sr having underfill-type tungsten bronze structure x Ba 1-x Nb 2 O 6 (SBN) system, which is SrNb 2 O 6 And BaNb 2 O 6 The solid solution range of the solid solution is x=0.26-0.87, and the solid solution has the characteristic of continuously adjustable Sr/Ba ratio, so that the electro-optic performance, the dielectric performance and the pyroelectric performance can be changed by adjusting the components, and the solid solution meets the requirements in different technical fields. The subject group found Gd-doped Sr 0.53 Ba 0.47 Nb 2 O 6 The (SBN) -based underfill tungsten bronze structure ferroelectric material has obviously higher polarization intensity than a pure SBN system, and is mainly caused by remarkable displacement and distortion of B-site ions in the center of a polarization unit due to the influence of an A-site electrochemical environment. However, the relaxation degree is not high, so that the breakdown field strength is low, and the further improvement of the energy storage performance is severely limited.
Disclosure of Invention
The invention aims to provide a rare earth doped tungsten bronze structure ceramic material with high energy storage property, which remarkably improves the energy storage density and efficiency.
The invention also aims to provide a preparation method of the rare earth doped tungsten bronze structure ceramic material with high energy storage.
The technical scheme adopted by the invention is that the rare earth doped tungsten bronze structure ceramic material with high energy storage property has the structural formula (Sr) 0.53-0.15x Ba 0.47 Gd x ) 1-y RE y Nb 2 O 6 Wherein RE is any one of Eu, la, sm, nd, dy, ce, er, pr, ho, yb, lu; the value of x is 0-0.1, and the value of y is 0.01-0.08.
The preparation method of the rare earth doped tungsten bronze structure ceramic material with high energy storage property is implemented according to the following steps:
step 1, according to (Sr) 0.53-0.15x Ba 0.47 Gd x ) 1-y RE y Nb 2 O 6 Respectively weighing BaCO with the purity of more than 99.00 percent 3 、SrCO 3 、Gd 2 O 3 、RE 2 O 3 、Nb 2 O 5 Fully mixing, ball milling and drying to obtain a raw material mixture;
step 2, presintering the raw material mixture for 2-6 hours at 900-1250 ℃ to obtain presintering powder;
and step 3, granulating, tabletting and discharging glue from the presintered powder, and sintering to obtain the rare earth doped tungsten bronze structure ceramic material.
The present invention is also characterized in that,
in the step 1, the ball milling time is 16-24 hours; the drying temperature is 80-100 ℃ and the drying time is 12-24 hours.
In the step 3, the sintering temperature is 1280-1340 ℃ and the sintering time is 2-6 hours.
The beneficial effects of the invention are as follows: the A-site rare earth doped ceramic system inhibits abnormal growth of anisometric grains of the tungsten bronze structure ceramic, forms a compact ferroelectric energy storage material, reduces energy dissipation under an electric field, and in addition, the ceramic composition does not relate to Bi, na, K and other elements which are easy to volatilize in a 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.
Drawings
FIG. 1 is an XRD pattern of the ceramic materials prepared in comparative example 1, comparative example 2 and examples 1 to 5.
FIG. 2 is a surface topography of the ceramic materials prepared in comparative example 2 and examples 1 to 5;
FIG. 3a is a graph of the hysteresis loop at room temperature of the ceramic materials prepared in comparative example 1, comparative example 2 and examples 1-6;
FIG. 3b is a graph of the energy storage properties of the ceramic materials prepared in comparative example 1, comparative example 2 and examples 1-6;
FIG. 4 is a graph showing the maximum polarization intensity and remnant polarization enhancement of the ceramic materials prepared in comparative example 1, comparative example 2 and examples 1 to 6 and the difference therebetween;
FIG. 5a is a graph of dielectric constants and dielectric losses for the ceramic material prepared in comparative example 2 at different test frequencies;
FIG. 5b is a graph of dielectric constants and dielectric losses for the ceramic material prepared in example 4 at different test frequencies;
FIG. 6 is a dielectric spectrum at 1kHz of the ceramic materials prepared in comparative example 1, comparative example 2 and examples 1 to 5;
FIG. 7 is a graph showing the dielectric constant at room temperature at 1kHz for the ceramic materials prepared in comparative example 1, comparative example 2 and examples 1 to 5.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention relates to a rare earth doped tungsten bronze structure ceramic material with high energy storage property, which has the structural formula (Sr) 0.53- 0.15x Ba 0.47 Gd x ) 1-y RE y Nb 2 O 6 Wherein RE is any one of Eu, la, sm, nd, dy, ce, er, pr, ho, yb, lu; the value of x is 0-0.1, the value of y is 0.01 to 0.08;
preferably, x has a value of 0.03 and y has a value of 0.2.
In the tungsten bronze structure, the phase change type and the phase change dispersion degree can be continuously changed by changing the substitution of the A-site ions. The invention provides a method for improving the energy storage performance by regulating and controlling the relaxation characteristic of the A-bit disorder, promoting the microscopic domain to be changed into the polarized nano domain, and remarkably enhancing the breakdown strength.
The invention relates to a preparation method of a rare earth doped tungsten bronze structure ceramic material with high energy storage, which is implemented according to the following steps:
step 1, according to (Sr) 0.53-0.15x Ba 0.47 Gd x ) 1-y RE y Nb 2 O 6 Respectively weighing BaCO with the purity of more than 99.00 percent 3 、SrCO 3 、Gd 2 O 3 、RE 2 O 3 、Nb 2 O 5 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;
step 2, presintering the raw material mixture for 2-6 hours at 900-1250 ℃ to obtain presintering powder;
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 500 ℃ at 1 ℃/min for discharging glue, and sintering for 2-6 hours at 1280-1340 ℃ to obtain an A-site rare earth doped tungsten bronze structure ceramic material;
preferably, the presintered powder is sintered for 2 hours at 1320 ℃ after pelleting, tabletting and adhesive discharging.
By adding a catalyst to Sr 0.53 Ba 0.47 Nb 2 O 6 The rare earth elements are doped in the ceramic system, so that not only is the high energy storage density obtained, but also the energy storage efficiency is remarkably improved, and meanwhile, a composition design method for obtaining the high energy storage performance is provided.
Example 1
The invention relates to a preparation method of a rare earth doped tungsten bronze structure ceramic material with high energy storage, which is implemented according to the following steps:
step 1, according to (Sr) 0.485 Ba 0.47 Gd 0.03 ) 0.98 La 0.02 Nb 2 O 6 Respectively weighing SrCO with the purity of 99.00 percent 3 2.4350g BaCO with a purity of 99.00% 3 3.1291g of Nb with purity of 99.90% 2 O 5 9.1409g of La with purity of 99.99% 2 O 3 0.1119g of Gd with purity of 99.99% 2 O 3 0.1831g, 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;
step 2, placing the raw material mixture into an alumina crucible, compacting by an agate rod to make the compacted density of the agate rod be 1.5g/cm 3 Capping, placing in a resistance furnace, heating to 1100 ℃ at a heating rate of 3 ℃/min for presintering for 4 hours, naturally cooling to room temperature, discharging, grinding for 10 minutes by using a mortar, and sieving by using a 120-mesh sieve to obtain presintering powder;
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, preparing 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 the zirconia flat plate to 500 ℃ at the heating rate of 1 ℃/min, preserving heat for 2 hours, discharging glue, cooling to room temperature, heating to 1000 ℃ at the heating rate of 5 ℃/min, heating to 1330 ℃ at the heating rate of 3 ℃/min, and naturally cooling to room temperature along with a furnace to obtain the Gd-La co-doped tungsten bronze structure ferroelectric energy storage ceramic material.
Example 2
In step 1 of the present embodiment, according to (Sr) 0.485 Ba 0.47 Gd 0.03 ) 0.98 Nd 0.02 Nb 2 O 6 Respectively weighing SrCO with the purity of 99.00 percent 3 2.4344g BaCO with a purity of 99.00% 3 3.1283g of Nb with purity of 99.90% 2 O 5 0.1157g of Ta having a purity of 99.85% 2 O 5 3.4517g of Gd with purity of 99.99% 2 O 3 0.2828g, and the other steps are the same as in example 1, to obtain the Gd-Nd co-doped tungsten bronze structure ferroelectric energy storage ceramic material.
Example 3
In step 1 of the present embodiment, according to (Sr) 0.485 Ba 0.47 Gd 0.03 ) 0.98 Sm 0.02 Nb 2 O 6 Respectively weighing SrCO with the purity of 99.00 percent 3 2.4344g BaCO with a purity of 99.00% 3 3.1283g of Nb with purity of 99.90% 2 O 5 9.1386g Sm with purity of 99.999% 2 O 3 0.1197g Gd with purity of 99.99% 2 O 3 0.1830g, and the other steps are the same as in example 1, to obtain the Gd-Sm co-doped tungsten bronze structure ferroelectric energy storage ceramic material.
Example 4
In step 1 of the present embodiment, according to (Sr) 0.485 Ba 0.47 Gd 0.03 ) 0.98 Eu 0.02 Nb 2 O 6 Respectively weighing SrCO with the purity of 99.00 percent 3 2.4335g BaCO with a purity of 99.00% 3 3.1272g of Nb with purity of 99.90% 2 O 5 9.1355g Eu with purity of 99.999% 2 O 3 0.1208g Gd with 99.99% purity 2 O 3 0.1830g, and the other steps are the same as in example 1, to obtain the Gd-Eu co-doped tungsten bronze structure ferroelectric energy storage ceramic material.
Example 5
In step 1 of the present embodiment, according to (Sr) 0.485 Ba 0.47 Gd 0.03 ) 0.98 Dy 0.02 Nb 2 O 6 Respectively weighing SrCO with the purity of 99.00 percent 3 2.4323g and purity of 99.00%BaCO of (A) 3 3.1257g of Nb with purity of 99.90% 2 O 5 9.1310g Dy with purity of 99.90% 2 O 3 0.1281g of Gd with purity of 99.99% 2 O 3 0.1829g, and the other steps are the same as in example 1, to obtain the Gd-Dy co-doped tungsten bronze structure ferroelectric energy storage ceramic material.
Example 6
In step 1 of the present embodiment, the following Sr is used 0.455 Ba 0.47 Sm 0.05 Nb 2 O 6 Respectively weighing SrCO with the purity of 99.00 percent 3 2.3365g BaCO with a purity of 99.00% 3 2.3005g of Nb with purity of 99.90% 2 O 5 9.1627g Sm with purity of 99.99% 2 O 3 0.3002g, the other steps are the same as in example 1, to obtain a rare earth Sm doped tungsten bronze structure ferroelectric energy storage ceramic material.
Comparative example 1
According to Sr 0.53 Ba 0.47 Nb 2 O 6 Respectively weighing SrCO with the purity of 99.00 percent 3 2.7017g BaCO with a purity of 99.00% 3 3.2026g of Nb with purity of 99.90% 2 O 5 9.0956g, the other steps are the same as in example 1, to give Sr 0.53 Ba 0.47 Nb 2 O 6 A ceramic material.
Comparative example 2
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 tungsten bronze structure ferroelectric energy storage ceramic material.
The ceramic materials prepared in the above comparative examples 1 and 2 and examples 1 to 6 were XRD tested by using a D/max-2200X-ray diffractometer (manufactured by Japanese society Co.), tested for ferroelectric properties by using a ferroelectric workstation and a connection temperature control device (THMS 600), and evaluated for energy storage characteristics, respectivelyThe results are shown in FIGS. 1 to 4. As can be seen from FIG. 1, the ceramic materials prepared in comparative example 1, comparative example 2 and examples 1 to 5 are all pure tetragonal tungsten bronze phases. As can be seen from fig. 2, the Gd and RE co-doped ceramic samples are relatively dense, and the proportion of equiaxed grains is significantly increased. As can be seen from FIG. 3a, comparative example 2 is prepared by adding Sr to a steel sheet 0.53 Ba 0.47 Nb 2 O 6 Gd doped in ceramic material can raise polarization intensity of ceramic material, but its electric field intensity is weaker, and the invention adopts Sr 0.485 Ba 0.47 Gd 0.03 Nb 2 O 6 RE doped in the ceramic material not only enhances polarization and electric field intensity of the ceramic material, but also reduces electric hysteresis loop of the ceramic material relative to comparative example 2, which has the most excellent energy storage density and efficiency as shown in FIG. 3b, and has a breakdown field strength of 520kV cm in example 3 -1 The energy storage performance at room temperature is 8.2J cm -3 The recoverable energy storage density is 7.3J cm -3 The efficiency was 90%, and the maximum polarization was 38.95. Mu.C.cm as shown in FIG. 4 -2 By obtaining an optimal balance between polarization and breakdown field strength, optimal energy storage performance is obtained.
The ceramic materials prepared in comparative example 1, comparative example 2 and examples 1 to 4 were polished to a thickness of 0.5 to 0.6mm on the surface thereof by using 320 mesh, 800 mesh and 1500 mesh sandpaper in this order, and then silver paste with a thickness of 0.01 to 0.03mm was coated on the upper and lower surfaces of the ceramic, and the ceramic materials were placed in a resistance furnace and heat-preserved for 30 minutes at 840 ℃. Ceramic dielectric properties were measured using HIOKI3532-50 and Agilent 4980A precision impedance analyzer (manufactured by Agilent technologies Co., ltd.) and the like, and the results are shown in FIGS. 5 to 7. As can be seen from FIGS. 5 to 7, compared with the ceramic materials of comparative examples 1 and 2, the relaxation of the ceramic is obviously enhanced by doping rare earth RE in the ceramic material, and when the value of x is 0.03 and the value of y is 0.02, the dielectric constant of the material at room temperature is obviously enhanced and the Curie temperature is near the room temperature.
The rare earth doped Sr prepared by the invention 0.53 Ba 0.47 Nb 2 O 6 The relaxation of the ceramic material is obviously enhanced, and the introduction of A-site non-equivalent ions induces the distortion of the polarization unit BO6 octahedron, and simultaneously causes the disordered distribution and formation of ionsThe local electric field and the elastic field are easy to break the long-range distribution of the ferroelectric domains to form nano polarized micro domains, and the breakdown resistance strength of the material is remarkably improved, namely, the high energy storage density and the high efficiency are realized. Unfilled Sr is regulated and controlled by A-bit disorder 0.53 Ba 0.47 Nb 2 O 6 The relaxation characteristic of the ceramic material promotes the microscopic domains to evolve into polarized nano domains, can obviously enhance the breakdown strength, and is further beneficial to improving the energy storage performance.
Claims (1)
1. The preparation method of the rare earth doped tungsten bronze structure ceramic material with high energy storage performance is characterized by comprising the following steps of:
step 1, according to (Sr) 0.485 Ba 0.47 Gd 0.03 ) 0.98 La 0.02 Nb 2 O 6 Respectively weighing SrCO with the purity of 99.00 percent 3 2.4350g BaCO with a purity of 99.00% 3 3.1291g of Nb with purity of 99.90% 2 O 5 9.1409g of La with purity of 99.99% 2 O 3 0.1119g of Gd with purity of 99.99% 2 O 3 0.1831g, 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;
step 2, placing the raw material mixture into an alumina crucible, compacting by an agate rod to make the compacted density of the agate rod be 1.5g/cm 3 Capping, placing in a resistance furnace, heating to 1100 ℃ at a heating rate of 3 ℃/min for presintering for 4 hours, naturally cooling to room temperature, discharging, grinding for 10 minutes by using a mortar, and sieving by using a 120-mesh sieve to obtain presintering powder;
and 3, adding a polyvinyl alcohol aqueous solution with the mass fraction of 5% into the presintered powder, granulating, sieving with a 100-mesh sieve to prepare spherical powder particles, putting the spherical powder particles into a stainless steel die with the diameter of 15mm, pressing the spherical powder 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, discharging glue, cooling to room temperature, heating to 1000 ℃ at the heating rate of 5 ℃/min, heating to 1330 ℃ at the heating rate of 3 ℃/min, sintering for 2 hours, and naturally cooling to room temperature along with a furnace to obtain the Gd-La co-doped tungsten bronze structure ferroelectric energy storage ceramic material.
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