CN112430084A - NBT-BT-based relaxation ferroelectric ceramic thin film material with high electric field strength resistance and high energy storage density and preparation method thereof - Google Patents
NBT-BT-based relaxation ferroelectric ceramic thin film material with high electric field strength resistance and high energy storage density and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a NBT-BT based relaxation ferroelectric ceramic film material with high electric field strength resistance and high energy storage density and a preparation method thereof, belonging to the technical field of dielectric ceramic material preparation. The invention discloses a chemical composition of 0.6(0.94 Na)0.5Bi0.5TiO3‑0.06BaTiO3)‑0.4(Sr0.7Bi0.2TiO3)‑0.1％Dy2O3(NBT-BT-40SBT-Dy) with high electric field strength resistance and high energy storage density. The NBT-BT based relaxation ferroelectric ceramic thin film material has the following properties: (1) the shape of the electric hysteresis loop is fine, the characteristics of a relaxation ferroelectric are shown, and the electric field strength can reach 270 kV/cm; (2) the total energy storage density and the effective energy storage density increase with the increase of the electric field; (3) the energy storage efficiency is more than 73%.
Description
Technical Field
The invention belongs to the technical field of dielectric ceramic material preparation, and particularly relates to a NBT-BT based relaxation ferroelectric ceramic film material with high electric field strength resistance and high energy storage density and a preparation method thereof.
Background
With the deep development of global social economy, the energy crisis is more and more serious, and the development and utilization of new energy technology becomes the key of the development of human society. The dielectric ceramic has great advantages in power density and service life due to good temperature, frequency stability and safety, and becomes an excellent candidate capacitor material. However, the energy storage density of the dielectric ceramic is generally not high, and it is difficult to meet the requirement of miniaturization of the pulse power device, and how to greatly improve the energy storage density of the dielectric ceramic has become one of the hot spots of research in the field of functional ceramics in recent years.
The NBT-BT based energy storage ceramic has high saturation polarization capability, lower coercive field and low dielectric loss, and is a potential material of an excellent ceramic capacitor. However, the NBT-BT based energy storage ceramic prepared by the traditional compaction forming-solid phase sintering process has coarse and uneven crystal grains, so that the NBT-BT based energy storage ceramic has lower electric field strength, generally about 100kV/cm, and thus the NBT-BT based energy storage ceramic has low energy storage density and limits the production application of the NBT-BT based energy storage ceramic. Therefore, how to effectively improve the electric field resistance/energy storage density of the NBT-BT based energy storage ceramic is one of the key problems which need to be solved urgently and are widely applied.
In order to improve the electric field strength of the NBT-BT based energy storage ceramic, the current research reports mainly focus on the aspects of sintering process, doping modification and the like, and the defects of insufficient improvement amplitude, low benefit and the like exist, so the research for improving the electric field strength and the energy storage density of the NBT-BT based energy storage ceramic by adjusting the blank making process before solid-phase sintering is very important.
Disclosure of Invention
In view of the above, the present invention provides an NBT-BT based relaxed ferroelectric ceramic thin film material with high electric field strength resistance and high energy storage density; the second purpose of the invention is to provide a preparation method of NBT-BT based relaxation ferroelectric ceramic film material with high electric field strength resistance and high energy storage density.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the NBT-BT based relaxation ferroelectric ceramic thin film material with high electric field strength resistance and high energy storage density has the chemical composition of 0.6(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.4(Sr0.7Bi0.2TiO3)-0.1％Dy2O3。
Preferably, the thickness of the NBT-BT based relaxation ferroelectric ceramic thin film material is 0.07-0.1 mm.
Preferably, the relaxor ferroelectric ceramic material has an effective energy storage density at room temperature of 4.83J/cm at an electric field of 270kV/cm3(ii) a The energy storage efficiency between 10 kV/cm and 270kV/cm is more than or equal to 78 percent.
2. The preparation method of the relaxor ferroelectric ceramic material comprises the following steps:
(1) SrCO is mixed according to a molar ratio of 7:2:103、Bi2O3And TiO2Mixing, ball milling to obtain mixture, oven drying, grinding, sieving, pre-sintering at 850 deg.C, keeping the temperature for 150min, cooling to room temperature, and ball milling again to obtain (Sr)0.7Bi0.2)TiO3；
(2) Mixing Na according to a molar ratio of 47:47:12:2002CO3、Bi2O3、BaCO3With TiO2Mixing, ball milling to obtain mixture, oven drying, grinding, sieving, pre-sintering at 900 deg.C, maintaining the temperature for 150min, cooling to room temperature, ball milling again to obtain 0.94Na0.5Bi0.5TiO3-0.06BaTiO3；
(3) The (Sr) prepared in the step (1) is mixed according to the molar ratio of 2:30.7Bi0.2)TiO3And 0.94Na prepared in the step (2)0.5Bi0.5TiO3-0.06BaTiO3Mixing, and adding 0.1 wt% dysprosium oxide (Dy)2O3) Mixing, ball milling, oven drying, grinding, and sieving to obtain 0.6(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.4(Sr0.7Bi0.2TiO3)-0.1％Dy2O3Powder (NBT-BT-40SBT-Dy powder);
(4) adding a PVA (polyvinyl acetate) binder into the product (NBT-BT-40SBT-Dy powder) prepared in the step (3), and placing the mixture into a ball milling tank for ball milling;
(5) drying the slurry subjected to ball milling in the step (4) to be pasty, and then rolling to form a strip-shaped NBT-BT-40SBT-Dy green body;
(6) drying the banded NBT-BT-40SBT-Dy green compact in a moisture-preserving box with the temperature of 30 ℃ and the relative humidity of 65%;
(7) and cutting, removing the glue and sintering the dried NBT-BT-40SBT-Dy green body to obtain the NBT-BT based relaxation ferroelectric ceramic film material.
Preferably, the SrCO3、Bi2O3、TiO2、Na2CO3、BaCO3And Dy2O3The purity of the product is not less than 99%, and the ball milling time is not less than 24 h.
Preferably, the sieving is performed by selecting a 60-mesh sieve.
Preferably, absolute ethyl alcohol and zirconia balls are added in the ball milling process.
Further preferably, the volume ratio of the absolute ethyl alcohol to the raw materials to be ball-milled in the ball milling process is 2: 1.
Further preferably, the volume ratio of the zirconia balls to the raw materials to be ball-milled in the ball milling process is 3: 2.
More preferably, the zirconia balls are composed of zirconia balls with the diameter of 10mm and the diameter of 5mm according to the number ratio of 1: 2.
Preferably, the time of ball milling is not less than 24 h.
Preferably, the rotating speed during ball milling is 270-330 r/min.
Preferably, the PVA binder in step (4) is prepared as follows: mixing glycerol, polyvinyl alcohol, boric acid, deionized water and absolute ethyl alcohol according to the volume mass ratio of 177:330:1.1:1900:700, ml: g: ml: ml, heating in a water bath, and stirring to obtain the PVA binder.
Further preferably, the mixing method is magnetic stirring.
Further preferably, the temperature of the water bath heating is 70-90 ℃.
Further preferably, the stirring time is 25-30 h.
Preferably, the PVA binder in the step (4) accounts for 30-45% of the powder (NBT-BT-40SBT-Dy powder) prepared in the step (3) in percentage by mass.
Preferably, the rolling in step (5) comprises the following specific processes: and turning and stirring the paste slurry into a cluster, rolling the green blank for multiple times at a rolling distance of 5mm in advance, then gradually reducing the rolling distance to reduce the thickness and compacting to obtain a strip-shaped NBT-BT-40SBT-Dy green blank with the thickness of 0.08-0.12 mm.
Preferably, the sheet of flat glass is placed on the flat glass sheet while being dried in step (6) and pressed with the same flat glass sheet.
Preferably, the drying time in the step (6) is 3-5 days.
Preferably, the rubber discharge in the step (7) is specifically as follows: the sheets formed by cutting are stacked together and then processed in a tubular muffle furnace.
Preferably, the sintering in step (7) is sintered in a box-type muffle furnace.
Preferably, the specific process of glue discharging and sintering in the step (7) is as follows:
firstly, raising the temperature from room temperature to 200 ℃ at the speed of 0.5 ℃/min and preserving the temperature for 4h, and then raising the temperature to 400 ℃ at the speed of 0.5 ℃/min and preserving the temperature for 4 h;
secondly, raising the temperature to 600 ℃ at a speed of 0.5 ℃/min, preserving the heat for 10 hours, cooling along with the furnace, and discharging the glue;
and finally, after the glue discharging is finished, transferring and spreading in a box type muffle furnace, raising the temperature to 1100-1200 ℃ at the speed of 3 ℃/min, preserving the temperature for 150min, cooling along with the furnace in the cooling process, and finishing sintering.
The invention has the beneficial effects that:
1. the invention discloses a NBT-BT based relaxation ferroelectric ceramic film material with high electric field strength resistance and high energy storage density, which comprises the following chemical compositions: 0.6(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.4(Sr0.7Bi0.2TiO3)-0.1％Dy2O3(abbreviated as NBT-BT-40 SBT-Dy). The NBT-BT based relaxation ferroelectric ceramic thin film material has the following properties: (1) the shape of the electric hysteresis loop is fine, the characteristics of a relaxation ferroelectric are shown, and the electric field strength can reach 270 kV/cm; (2) the total energy storage density and the effective energy storage density increase with the increase of the electric field; (3) the energy storage efficiency is more than 73%.
2. The invention also discloses a preparation method of the NBT-BT based relaxation ferroelectric ceramic film material with high electric field strength resistance and high energy storage density, and on one hand, the preparation method is simple and easy to operate, good in repeatability and high in yield, so that the production cost can be greatly reduced; on the other hand, the NBT-BT-40SBT-Dy ceramic material is prepared by using more PVA as an NBT-BT-40SBT-Dy powder carrier and using a rolling process, so that the density of the ceramic material is improved, and the grain size is reduced, thereby improving the electric field resistance of the NBT-BT-40SBT-Dy ceramic material to a great extent.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is an XRD pattern measured at room temperature of the NBT-BT based relaxed ferroelectric ceramic thin film material (NBT-BT-40SBT-Dy) prepared in example 1;
FIG. 2 is a room temperature hysteresis loop diagram of the NBT-BT based relaxed ferroelectric ceramic thin film material (NBT-BT-40SBT-Dy) prepared in example 1 at different electric field strengths;
FIG. 3 shows the variation of total energy storage density, effective energy storage density and energy storage efficiency with electric field strength at room temperature of the NBT-BT-based relaxed ferroelectric ceramic thin film material (NBT-BT-40SBT-Dy) prepared in example 1;
FIG. 4 is an XRD pattern measured at room temperature of the NBT-BT based relaxed ferroelectric ceramic thin film material (NBT-BT-40SBT-Dy) prepared in example 2;
FIG. 5 shows the dielectric constants of NBT-BT based relaxed ferroelectric ceramic thin film materials (NBT-BT-40SBT-Dy) prepared in example 2 at different frequencies;
FIG. 6 is a room temperature hysteresis loop diagram of the NBT-BT based relaxed ferroelectric ceramic thin film material (NBT-BT-40SBT-Dy) prepared in example 2 under different electric field strengths.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that, in the following embodiments, features in the embodiments may be combined with each other without conflict.
Example 1
A chemical composition of 0.6(0.94 Na) was prepared0.5Bi0.5TiO3-0.06BaTiO3)-0.4(Sr0.7Bi0.2TiO3)-0.1％Dy2O3The NBT-BT based relaxation ferroelectric ceramic film material (PVA content 35%) with high electric field strength resistance and high energy storage density of (NBT-BT-40SBT-Dy) comprises the following specific steps:
(1) 177ml of glycerol, 330g of polyvinyl alcohol, 1.1g of boric acid, 1900ml of deionized water and 700ml of absolute ethyl alcohol are mixed under magnetic stirring, and are heated in a water bath at 70 ℃ and stirred for 30 hours to obtain a PVA binder;
(2) SrCO with the purity of 99 percent is mixed according to the molar ratio of 7:2:103、Bi2O3And TiO2Mixing, ball milling to obtain mixture, oven drying, grinding, sieving, pre-sintering at 850 deg.C, keeping the temperature for 150min, cooling to room temperature, ball milling for more than 24 hr to obtain (Sr)0.7Bi0.2)TiO3；
(3) Push buttonMolar ratio of 47:47:12:200, mixing Na with purity of 99%2CO3、Bi2O3、BaCO3With TiO2Mixing, ball milling for more than 24h to obtain mixture, oven drying, grinding, sieving, pre-sintering at 900 deg.C, maintaining the temperature for 150min, cooling to room temperature, ball milling for more than 24h to obtain 0.94Na0.5Bi0.5TiO3-0.06BaTiO3；
(4) According to the molar ratio of 2:3, (Sr) prepared in the step (2)0.7Bi0.2)TiO3And 0.94Na prepared in step (3)0.5Bi0.5TiO3-0.06BaTiO3Mixing, and adding 0.1 wt% of dysprosium trioxide (Dy) with purity of 99% or more2O3) Mixing, ball milling for more than 24h to obtain a mixture, drying, grinding, and sieving with 60 mesh sieve to obtain NBT-BT-40SBT-Dy powder of 0.6(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.4(Sr0.7Bi0.2TiO3)-0.1％Dy2O3And (3) powder.
(5) Taking 100g of NBT-BT-40SBT-Dy powder in the step (4), adding 35g of PVA binder prepared in the step (1), and then placing the mixture into a ball milling tank, adding deionized water and carrying out ball milling for 72 hours;
(6) baking the ball-milled NBT-BT-40SBT-Dy slurry mixed with PVA in the step (5) to be pasty, then rolling the paste into a belt-shaped NBT-BT-40SBT-Dy green body (the specific rolling process comprises the steps of turning and stirring the paste mixed with PVA and in the shape of NBT-BT-40SBT-Dy pasty to be capable of being agglomerated into a whole, rolling the green body for multiple times at a rolling distance of 5mm in advance, and then gradually reducing the interval to roll to reduce the thickness and compact the green body to obtain the belt-shaped NBT-BT-40SBT-Dy green body with the thickness of 0.08-0.12 mm);
(7) firstly, placing the banded NBT-BT-40SBT-Dy green body obtained in the step (6) on a plane glass plate, pressing the banded NBT-BT-40SBT-Dy green body by using the same plane glass plate, and then drying the banded NBT-BT-40SBT-Dy green body in a moisture preservation box with the temperature of 30 ℃ and the relative humidity of 65% for 3 days;
(8) cutting the dried NBT-BT-40SBT-Dy green body in the step (7), removing the rubber (stacking the cut sheets together and then sintering in a tubular muffle furnace), and sintering (sintering in a box muffle furnace), wherein the concrete processes of rubber removal and sintering are as follows:
firstly, raising the temperature from room temperature to 200 ℃ at the speed of 0.5 ℃/min and preserving the temperature for 4h, and then raising the temperature to 400 ℃ at the speed of 0.5 ℃/min and preserving the temperature for 4 h;
secondly, raising the temperature to 600 ℃ at a speed of 0.5 ℃/min, preserving the heat for 10 hours, cooling along with the furnace, and discharging the glue;
and finally, after the glue discharging is finished, transferring and spreading in a box-type muffle furnace, raising the temperature to 1100 ℃ at the speed of 3 ℃/min, preserving the temperature for 150min, cooling along with the furnace in the cooling process, and finally obtaining the NBT-BT based relaxation ferroelectric ceramic film material (NBT-BT-40SBT-Dy) with the thickness of 0.07-0.1 mm after sintering.
The ball milling involved in the preparation process is carried out in the process of adding absolute ethyl alcohol and zirconia balls, wherein the volume ratio of the absolute ethyl alcohol to the raw materials to be ball milled is 2:1, the volume ratio of the zirconia balls to the raw materials to be ball milled is 3:2, and the zirconia balls are composed of zirconia balls with the diameter of 10mm and the diameter of 5mm according to the number ratio of 1: 2.
Example 2
A chemical composition of 0.6(0.94 Na) was prepared0.5Bi0.5TiO3-0.06BaTiO3)-0.4(Sr0.7Bi0.2TiO3)-0.1％Dy2O3The specific method of the NBT-BT based relaxation ferroelectric ceramic film material (PVA content is 40%) with high electric field strength resistance and high energy storage density of (NBT-BT-40SBT-Dy) is as follows:
(1) 177ml of glycerol, 330g of polyvinyl alcohol, 1.1g of boric acid, 1900ml of deionized water and 700ml of absolute ethyl alcohol are mixed under magnetic stirring, and the mixture is stirred in a water bath at 90 ℃ for 25 hours to obtain a PVA binder;
(2) SrCO with the purity of 99 percent is mixed according to the molar ratio of 7:2:103、Bi2O3And TiO2Mixing, ball milling to obtain mixture, oven drying, grinding, sieving, pre-sintering at 850 deg.C, keeping the temperature for 150min, cooling to room temperature, ball milling for more than 24 hr to obtain (Sr)0.7Bi0.2)TiO3；
(3) According to the molar ratio of 47:47:12:200, mixing Na with the purity of 99 percent2CO3、Bi2O3、BaCO3With TiO2Mixing, ball milling for more than 24h to obtain mixture, oven drying, grinding, sieving, pre-sintering at 900 deg.C, maintaining the temperature for 150min, cooling to room temperature, ball milling for more than 24h to obtain 0.94Na0.5Bi0.5TiO3-0.06BaTiO3；
(4) According to the molar ratio of 2:3, (Sr) prepared in the step (2)0.7Bi0.2)TiO3And 0.94Na prepared in step (3)0.5Bi0.5TiO3-0.06BaTiO3Mixing, and adding 0.1 wt% of dysprosium trioxide (Dy) with purity of 99% or more2O3) Mixing, ball milling for more than 24h to obtain a mixture, drying, grinding, and sieving with 60 mesh sieve to obtain NBT-BT-40SBT-Dy powder of 0.6(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.4(Sr0.7Bi0.2TiO3)-0.1％Dy2O3And (3) powder.
(5) Taking 100g of NBT-BT-40SBT-Dy powder in the step (4), adding 40g of PVA binder prepared in the step (1), and then placing the mixture into a ball milling tank, adding deionized water and carrying out ball milling for 72 hours;
(6) baking the ball-milled NBT-BT-40SBT-Dy slurry mixed with PVA in the step (5) to be pasty, then rolling the paste into a belt-shaped NBT-BT-40SBT-Dy green body (the specific rolling process comprises the steps of turning and stirring the paste mixed with PVA and in the shape of NBT-BT-40SBT-Dy pasty to be capable of being agglomerated into a whole, rolling the green body for multiple times at a rolling distance of 5mm in advance, and then gradually reducing the interval to roll to reduce the thickness and compact the green body to obtain the belt-shaped NBT-BT-40SBT-Dy green body with the thickness of 0.08-0.12 mm);
(7) placing the banded NBT-BT-40SBT-Dy green compact obtained in the step (6) on a plane glass plate, pressing the banded NBT-BT-40SBT-Dy green compact by using the same plane glass plate, and drying the banded NBT-BT-40SBT-Dy green compact in a moisture-preserving box at the temperature of 30 ℃ and the relative humidity of 65% for 5 days;
(8) cutting the NBT-BT-40SBT-Dy green blank obtained in the step (7), removing the rubber (stacking the cut sheets together and then sintering in a tubular muffle furnace), and sintering (sintering in a box muffle furnace), wherein the concrete processes of discharging and sintering are as follows:
firstly, raising the temperature from room temperature to 200 ℃ at the speed of 0.5 ℃/min and preserving the temperature for 4h, and then raising the temperature to 400 ℃ at the speed of 0.5 ℃/min and preserving the temperature for 4 h;
secondly, raising the temperature to 600 ℃ at a speed of 0.5 ℃/min, preserving the heat for 10 hours, cooling along with the furnace, and discharging the glue;
and finally, after the glue discharging is finished, transferring and spreading in a box-type muffle furnace, raising the temperature to 1200 ℃ at the speed of 3 ℃/min, preserving the temperature for 150min, cooling along with the furnace in the cooling process, and finally obtaining the NBT-BT based relaxation ferroelectric ceramic film material (NBT-BT-40SBT-Dy) with the thickness of 0.07-0.1 mm after sintering.
The ball milling involved in the preparation process is carried out in the process of adding absolute ethyl alcohol and zirconia balls, wherein the volume ratio of the absolute ethyl alcohol to the raw materials to be ball milled is 2:1, the volume ratio of the zirconia balls to the raw materials to be ball milled is 3:2, and the zirconia balls are composed of zirconia balls with the diameter of 10mm and the diameter of 5mm according to the number ratio of 1: 2.
And (3) performance testing:
the XRD pattern of the NBT-BT based relaxed ferroelectric ceramic thin film material (NBT-BT-40SBT-Dy, PVA content 35%) prepared in example 1 is shown in FIG. 1, and the room temperature hysteresis loop at different electric field strengths is shown in FIG. 2. As can be seen from FIG. 2, the hysteresis loop is slender, and shows the characteristics of a relaxor ferroelectric, and the electric field strength can reach 270 kV/cm. Under the electric field, the maximum polarization is 63.33 mu C/cm2The residual polarization is 6.01 mu C/cm2. 0.6(0.94 Na) prepared in example 10.5Bi0.5TiO3-0.06BaTiO3)-0.4(Sr0.7Bi0.2TiO3)-0.1％Dy2O3The changes of the total energy storage density, the effective energy storage density and the energy storage efficiency of the material at room temperature along with the electric field intensity are shown in figure 3. As can be seen from FIG. 3, the total and effective energy storage densities increased with increasing electric field, reaching a maximum at 270kV/cm electric field, 6.28J/cm each3And 4.83J/cm3. Under the electric field not higher than 270kV/cm, the energy storage efficiency is always kept above 78%.
NBT-BT based relaxed ferroelectric ceramic thin film material (NBT-BT-40SBT-Dy, PVA content 40%)) The XRD patterns of (A) and (B) are shown in FIG. 4, and the dielectric constants at different frequencies and the room temperature hysteresis loops at different electric field strengths are shown in FIG. 5 and FIG. 6, respectively. The dielectric constants of the NBT-BT-40SBT-Dy material prepared in example 2 at different frequencies are shown in FIG. 5, and have very low dielectric loss while keeping a high dielectric constant; as can be seen from FIG. 6, the room temperature hysteresis loop is also thin and shows the characteristics of a relaxor ferroelectric, and the electric field strength can reach 290 kV/cm. Under the electric field, the maximum polarization is 71.31 mu C/cm2And the residual polarization is 7.83 mu C/cm2. In addition, the total energy storage density and the effective energy storage density are increased along with the increase of the electric field and reach the maximum in the 290kV/cm electric field, and the effective energy storage density is 5.7J/cm3. Under the electric field not higher than 290kV/cm, the energy storage efficiency is always kept above 73%.
In conclusion, the successful preparation by the preparation method of the invention can obtain the chemical composition of 0.6(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.4(Sr0.7Bi0.2TiO3)-0.1％Dy2O3The NBT-BT-based relaxation ferroelectric ceramic thin film material with high electric field resistance strength and high energy storage density of (NBT-BT-40SBT-Dy) has the following properties: (1) the shape of the electric hysteresis loop is fine, the characteristics of a relaxation ferroelectric are shown, and the electric field strength can reach 270 kV/cm; (2) the total energy storage density and the effective energy storage density increase with the increase of the electric field; (3) the energy storage efficiency is more than 73%. In addition, the invention discloses a preparation method of the NBT-BT based relaxation ferroelectric ceramic film material with high electric field strength resistance and high energy storage density, and on one hand, the preparation method is simple and easy to operate, good in repeatability and high in yield, so that the production cost can be greatly reduced; on the other hand, the NBT-BT-40SBT-Dy ceramic material is prepared by using more PVA as an NBT-BT-40SBT-Dy powder carrier and using a rolling process, so that the density of the ceramic material is improved, and the grain size is reduced, thereby improving the electric field resistance strength of the NBT-BT-40SBT-Dy ceramic to a great extent.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. The NBT-BT based relaxation ferroelectric ceramic thin film material with high electric field strength resistance and high energy storage density is characterized in that the chemical composition of the NBT-BT based relaxation ferroelectric ceramic material NBT-BT-40SBT-Dy is 0.6(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.4(Sr0.7Bi0.2TiO3)-0.1％Dy2O3。
2. The method of preparing a relaxed ferroelectric ceramic thin film material of claim 1, comprising the steps of:
(1) SrCO is mixed according to a molar ratio of 7:2:103、Bi2O3And TiO2Mixing, ball milling to obtain mixture, oven drying, grinding, sieving, pre-sintering at 850 deg.C, keeping the temperature for 150min, cooling to room temperature, and ball milling again to obtain (Sr)0.7Bi0.2)TiO3；
(2) Mixing Na according to a molar ratio of 47:47:12:2002CO3、Bi2O3、BaCO3With TiO2Mixing, ball milling to obtain mixture, oven drying, grinding, sieving, pre-sintering at 900 deg.C, maintaining the temperature for 150min, cooling to room temperature, and ball milling to obtain (0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)；
(3) The (Sr) prepared in the step (1) is mixed according to the molar ratio of 2:30.7Bi0.2)TiO3(0.94 Na) prepared in step (2)0.5Bi0.5TiO3-0.06BaTiO3) Mixing, adding dysprosium oxide 0.1 wt%, ball milling to obtain mixture, oven drying, grinding, and sieving to obtain 0.6(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.4(Sr0.7Bi0.2TiO3)-0.1％Dy2O3Powder;
(4) adding a PVA binder into the powder prepared in the step (3), and placing the powder in a ball milling tank for ball milling;
(5) drying the slurry subjected to ball milling in the step (4) to be pasty, and then rolling to form a strip-shaped NBT-BT-40SBT-Dy green body;
(6) drying the banded NBT-BT-40SBT-Dy green compact in a moisture-preserving box with the temperature of 30 ℃ and the relative humidity of 65%;
(7) and cutting, removing the glue and sintering the dried NBT-BT-40SBT-Dy green body to obtain the NBT-BT based relaxation ferroelectric ceramic film material.
3. The method of claim 2, wherein the SrCO is3、Bi2O3、TiO2、Na2CO3、BaCO3And Dy2O3The purity of (A) is not less than 99%.
4. The method according to claim 2, wherein the PVA binder in the step (4) is prepared by: mixing glycerol, polyvinyl alcohol, boric acid, deionized water and absolute ethyl alcohol according to the volume mass ratio of 177:330:1.1:1900:700, ml: g: ml: ml, heating in a water bath, and stirring to obtain the PVA binder.
5. The method of claim 4, wherein the mixing is performed by magnetic stirring; the water bath heating temperature is 70-90 ℃; the stirring time is 25-30 h.
6. The preparation method according to claim 4, wherein the PVA binder in the step (4) accounts for 30-45% of the mass fraction of the powder prepared in the step (3).
7. The preparation method according to claim 2, wherein the rolling in the step (5) comprises the following specific processes: and turning and stirring the paste slurry into a cluster, repeatedly rolling the green blank in advance at a rolling distance of 5mm, then gradually reducing the rolling distance to reduce the thickness and compacting to obtain a strip-shaped NBT-BT-40SBT-Dy green blank with the thickness of 0.08-0.12 mm.
8. The production method according to claim 2, wherein the flat glass plate is placed while being dried in the step (6) and is pressed with the same flat glass plate; the drying time is 3-5 days.
9. The preparation method according to claim 2, wherein the gel discharging in the step (7) is specifically: stacking the sheets formed by cutting together and then performing in a tubular muffle furnace; the sintering is carried out in a box-type muffle furnace.
10. The preparation method according to claim 9, wherein the concrete process of the gel discharging and sintering in the step (7) is as follows:
firstly, raising the temperature from room temperature to 200 ℃ at the speed of 0.5 ℃/min and preserving the temperature for 4h, and then raising the temperature to 400 ℃ at the speed of 0.5 ℃/min and preserving the temperature for 4 h;
secondly, raising the temperature to 600 ℃ at a speed of 0.5 ℃/min, preserving the heat for 10 hours, cooling along with the furnace, and discharging the glue;
and finally, after the glue discharging is finished, transferring and spreading in a box type muffle furnace, raising the temperature to 1100-1200 ℃ at the speed of 3 ℃/min, preserving the temperature for 150min, cooling along with the furnace in the cooling process, and finishing sintering.
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