CN115881430A - High-energy-density sodium bismuth titanate-based dielectric ceramic capacitor and preparation method thereof - Google Patents

High-energy-density sodium bismuth titanate-based dielectric ceramic capacitor and preparation method thereof Download PDF

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CN115881430A
CN115881430A CN202211542365.8A CN202211542365A CN115881430A CN 115881430 A CN115881430 A CN 115881430A CN 202211542365 A CN202211542365 A CN 202211542365A CN 115881430 A CN115881430 A CN 115881430A
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powder
bismuth titanate
ceramic capacitor
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sodium bismuth
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娄晓杰
康瑞瑞
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Xian Jiaotong University
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Abstract

The invention discloses a high-energy-density sodium bismuth titanate-based dielectric ceramic capacitor and a preparation method thereof, wherein the chemical composition formula of the ceramic material is (1-x) (0.6 Bi) 0.5 Na 0.5 TiO 3 ‑0.4Sr 0.7 Bi 0.2 TiO 3 )‑xLaMg 0.5 Ti 0.5 O 3 Wherein x =0.04-0.12, x represents LaMg 0.5 Ti 0.5 O 3 In terms of molar ratio of (a). The energy storage performance of the sodium bismuth titanate-based dielectric ceramic capacitor is optimized. The final experiment result shows that the high-energy-density sodium bismuth titanate-based dielectric ceramic capacitor of the invention presents a slender electric hysteresis loop, obtains excellent energy storage performance under the action of a lower external electric field, and has excellent temperature stability (-50-200 ℃), frequency stability (2-100 Hz) and anti-fatigue property (10) 5 Second).

Description

High-energy-density sodium bismuth titanate-based dielectric ceramic capacitor and preparation method thereof
Technical Field
The invention belongs to the technical field of functional ceramic materials, and relates to a sodium bismuth titanate-based dielectric ceramic capacitor with high energy density and a preparation method thereof.
Background
In recent decades, with the rapid increase of energy consumption and the strict restriction of greenhouse gas emission, the vigorous development of renewable, efficient and clean energy storage industry is promoted. The dielectric capacitor based on the dielectric material has high charge-discharge speed and good operation reliability, and is widely applied to energy storage equipment as a key device of an electronic system.
The dielectric capacitor includes a film capacitor and a ceramic capacitorThe breakdown field strength is high, so that the energy density is ultrahigh, for example, the energy storage density of a sodium bismuth titanate-based flexible ferroelectric film (publication No. CN 113690053A) prepared by Shenzhen advanced technology research institute of Zhongkoji is 24.26J/cm 3 The energy storage efficiency is 71.93%. However, the small volume of the film is low, and therefore the energy density actually stored is extremely limited. The ceramic capacitor is widely concerned due to simple preparation process and good thermal stability, and has been developed in recent years, for example, the breakdown field strength of tungsten bronze structure ferroelectric energy storage ceramic (published No. CN 114605151A) prepared by professor of Western's university of Engineers Sun Shaodong can reach 470kV/cm, and the energy storage density is 6.23J/cm 3 The energy storage efficiency was 83.8%. However, the high energy storage densities (> 5J/cm) obtained in recent studies 3 ) In most cases, an extremely high external electric field (400-1000 kV/cm) is applied. However, when the electronic component operates in the ultra-high electric field, a large amount of heat is easily released, the service life is greatly reduced, and the normal operation of the equipment is not facilitated. In addition, the higher energy conversion efficiency helps to avoid damage to the device due to thermal lag. Therefore, it is urgent to obtain excellent energy storage density and energy storage efficiency under the action of a low external electric field.
Disclosure of Invention
The invention aims to solve the key technical problem of providing a sodium bismuth titanate-based dielectric ceramic capacitor with high energy density and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a high energy density sodium bismuth titanate based dielectric ceramic capacitor comprises the following chemical components:
(1-x)(0.6Bi 0.5 Na 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 )-xLaMg 0.5 Ti 0.5 O 3 wherein x represents LaMg 0.5 Ti 0.5 O 3 The value of x is in the range of 0.04-0.12.
Preferably, x is 0.08.
The preparation method of the sodium bismuth titanate-based dielectric ceramic capacitor with high energy density comprises the following steps:
uniformly mixing the raw material powder to obtain initial powder;
presintering the initial powder at 850-880 ℃ for 2-4h to obtain presynthesized ceramic powder;
uniformly mixing the pre-synthesized ceramic powder, granulating, pre-pressing and forming, and carrying out cold isostatic pressing to obtain a ceramic green body;
and (3) carrying out binder removal on the ceramic green body, then sintering for 2-4h at 1130-1150 ℃, and naturally cooling to room temperature along with the furnace to obtain the high-energy-density sodium bismuth titanate-based dielectric ceramic capacitor.
Preferably, the raw material powder includes Bi 2 O 3 Powder, na 2 CO 3 Powder, la 2 O 3 Powder, srCO 3 Powder, mgO powder and TiO 2 And (3) powder.
Preferably, when the raw material powder is uniformly mixed, the raw material powder is uniformly mixed by adopting a ball milling mode, the ball milling rotating speed is 400-450r/min, and the ball milling time is 10-12h.
Preferably, when the pre-synthesized ceramic powder is uniformly mixed, the pre-synthesized ceramic powder is uniformly mixed by adopting a ball milling mode, the ball milling rotating speed is 400-450r/min, and the ball milling time is 10-12h.
Preferably, a polyvinyl alcohol solution is used as a binder in the granulation.
Preferably, when the ceramic green body is subjected to rubber discharge, the rubber discharge temperature is 500-600 ℃, and the rubber discharge time is 5-10h.
Preferably, the pressure of the pre-pressing molding is controlled to be 2-4MPa.
Preferably, the cold isostatic pressing pressure is 200-230MPa, and the dwell time is 1-3min.
The BNT-based ceramic capacitor with high energy storage performance prepared by the invention can be used in the field of integrated and miniaturized electronic components.
Compared with the prior art, the invention has the following beneficial effects:
the invention is applied to a high-polarity substrate of 0.6BNT-0.4SBT (i.e., (0.6 Bi) 0.5 Na 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 ) In (1) introductionLow dielectric loss perovskite type third component LMT (i.e. LaMg) 0.5 Ti 0.5 O 3 ) The energy storage performance of the sodium bismuth titanate-based dielectric ceramic capacitor is optimized. The final experimental result shows that the high-energy-density sodium bismuth titanate-based dielectric ceramic capacitor of the invention presents a slender hysteresis loop, obtains excellent energy storage performance under the action of a lower external electric field, and has excellent temperature stability (-50-200 ℃), frequency stability (2-100 Hz) and anti-fatigue property (10) 5 Second).
Drawings
FIG. 1 is an X-ray diffraction pattern of a ceramic composition prepared according to comparative example and all examples of the present invention;
FIG. 2 (a) is a scanning electron micrograph of a ceramic prepared in comparative example; FIG. 2 (b) is a scanning electron micrograph of a ceramic prepared according to example 1 of the present invention; FIG. 2 (c) is a scanning electron micrograph of a ceramic prepared according to example 2 of the present invention; FIG. 2 (d) is a SEM photograph of a ceramic prepared in example 3 of the present invention;
FIG. 3 (a) is a dielectric temperature spectrum of a ceramic prepared by a comparative example; FIG. 3 (b) is a dielectric temperature spectrum of the ceramic prepared in example 1 of the present invention; FIG. 3 (c) is a dielectric temperature spectrum of the ceramic prepared in example 2 of the present invention; FIG. 3 (d) is a dielectric temperature spectrum of a ceramic prepared in example 3 of the present invention;
FIG. 4 is a hysteresis loop of ceramics prepared by comparative example and all examples of the present invention at room temperature;
fig. 5 is a temperature swing hysteresis loop for a ceramic composition of x =0.08 made in example 2 of the present invention;
fig. 6 is a frequency conversion hysteresis loop for a x =0.08 ceramic composition made in example 2 of the present invention;
fig. 7 is a fatigue hysteresis loop for the x =0.08 ceramic composition prepared in example 2 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. It should be noted that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The invention is prepared by adding bismuth sodium titanate-strontium bismuth titanate (0.6B)i 0.5 Na 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 Abbreviated as 0.6BNT-0.4 SBT) ceramic system is introduced with a perovskite third component LaMg with low dielectric loss 0.5 Ti 0.5 O 3 (abbreviated as LMT) to finally obtain the sodium bismuth titanate based energy storage ceramic with high energy density.
Specifically, the sodium bismuth titanate-based dielectric ceramic capacitor with high energy density provided by the invention comprises the following chemical components:
(1-x)(0.6Bi 0.5 Na 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 )-xLaMg 0.5 Ti 0.5 O 3 wherein, the value range of x is 0.04-0.12.
The high-energy-density sodium bismuth titanate-based dielectric ceramic capacitor is prepared by a solid-phase reaction method, and the preparation method comprises the following steps:
step 1, adding Bi 2 O 3 Powder, na 2 CO 3 Powder, la 2 O 3 Powder, srCO 3 Powder, mgO powder and TiO 2 Performing ball milling and uniform mixing on the powder to obtain initial powder, wherein the ball milling speed is 400-450r/min, and the ball milling time is 10-12h; wherein Bi is added 2 O 3 Powder, na 2 CO 3 Powder, la 2 O 3 Powder, srCO 3 Powder, mgO powder and TiO 2 The purity of the powder is more than 99 percent;
step 2, placing the initial powder into a muffle furnace, and presintering for 2-4h at 850-880 ℃ to obtain presynthesized ceramic powder;
step 3, uniformly mixing the ceramic powder, granulating, pre-pressing and forming, and carrying out cold isostatic pressing to obtain a ceramic green body; wherein, when the ceramic powder is mixed uniformly, the ceramic powder is mixed uniformly by adopting a ball milling mode, the ball milling speed is 400-450r/min, and the ball milling time is 10-12h; during granulation, polyvinyl alcohol (PVA) solution with 6 mass percent of solute is used as a binder, the pressure of pre-pressing molding is controlled to be 2-4Mpa, the pressure of cold isostatic pressing is 200-230Mpa, and the pressure maintaining time is 1-3min;
and 4, placing the ceramic green body into a muffle furnace, discharging glue for 5-10h at 500-600 ℃, removing polyvinyl alcohol, sintering for 2-4h at 1130-1150 ℃, and naturally cooling to room temperature along with the furnace to obtain the high-energy-density sodium bismuth titanate-based dielectric ceramic capacitor.
The preparation method also comprises the following steps: and (5) sputtering metal electrodes on the upper surface and the lower surface of the high-energy-density sodium bismuth titanate-based dielectric ceramic capacitor prepared in the step (4) so as to facilitate wiring.
Comparative example
The chemical composition of the bismuth titanate sodium-based ceramic of the comparative example is 0.6BNT-0.4SBT, namely x =0, and the specific preparation flow is as follows:
step 1, selecting Bi with the purity higher than 99% from Alfa Aesar manufacturers 2 O 3 ,Na 2 CO 3 ,SrCO 3 And TiO 2
Step 2, calculating the mass of the raw materials to be weighed according to the stoichiometric ratio, then weighing the 4 raw materials by using an electronic balance, placing the raw materials in a 50mL polytetrafluoroethylene ball milling tank, adding 30g of agate round beads and 25mL of absolute ethyl alcohol as ball milling media, wherein the ball milling speed is 450r/min, and the ball milling time is 10 hours;
step 3, pouring the slurry subjected to ball milling into an evaporation pan, and placing the evaporation pan in an oven to be dried for 10 hours at the temperature of 60 ℃;
step 4, putting the dried powder into an alumina crucible, covering the alumina crucible, putting the alumina crucible into a muffle furnace for presintering to obtain presynthesized powder, setting the heating rate to be 2 ℃/min, the presintering temperature to be 880 ℃, keeping the temperature for 3 hours, and then naturally cooling along with the furnace;
step 5, putting the powder into a ball milling tank again for secondary ball milling, wherein agate round beads and absolute ethyl alcohol are still used as ball milling media in the process, the ball milling speed is 450r/min, and the ball milling time is 10 hours;
step 6, pouring the slurry subjected to ball milling into an evaporation pan, covering to prevent impurities from entering, and drying in an oven at 80 ℃ for 8 hours;
step 7, taking out the dried powder, placing the powder in a mortar for full grinding, then dropwise adding 6wt% of PVA for granulation until the mixture is uniform, then sieving the mixture through a 100-mesh sieve, and bagging the mixture for later use;
step 8, weighing 0.25g of the powder, filling the powder into a cylindrical die with the diameter of 10mm, and performing prepressing molding on a powder tablet press;
step 9, putting the pre-pressed and molded green body into a butyronitrile glove, vacuumizing, and then putting into a cold isostatic press, and keeping the pressure for 3min under the condition of 230MPa to obtain a compact green body;
and step 10, placing the green body in a muffle furnace for binder removal, preserving heat for 8 hours at 600 ℃, then starting sintering, preserving heat for 3 hours at the temperature rise rate of 3 ℃/min and the sintering temperature of 1150 ℃, and then naturally cooling along with the furnace. It should be noted that since Bi and Na are volatile elements, the ceramic green body needs to be covered with the powder thereof during sintering to reduce volatilization;
step 11, grinding and polishing the sintered ceramic samples on 250-mesh, 800-mesh and 2000-mesh sandpaper respectively;
step 12, coating silver on the upper surface and the lower surface of the sample, and then putting the sample into a muffle furnace for heat preservation at 650 ℃ for 20min for testing the dielectric property; sputtering a Pt electrode on the surface of the sample by using a magnetron sputtering instrument for testing the electric hysteresis loop; other properties were obtained by directly using a sample sintered into porcelain.
Example 1
The chemical composition of the sodium bismuth titanate-based dielectric ceramic capacitor with high energy density provided by the embodiment is 0.96 (0.6 BNT-0.4 SBT) -0.04LMT, and the specific preparation flow is as follows:
step 1, selecting Bi with the purity higher than 99% from Alfa Aesar manufacturers 2 O 3 ,Na 2 CO 3 ,La 2 O 3 ,SrCO 3 MgO and TiO 2
Step 2, calculating the mass of the raw materials to be weighed according to the stoichiometric ratio, then weighing the 6 raw materials by using an electronic balance, placing the raw materials in a 50mL polytetrafluoroethylene ball milling tank, adding 30g of agate round beads and 25mL of absolute ethyl alcohol as ball milling media, wherein the ball milling speed is 400r/min, and the ball milling time is 11 hours;
step 3, pouring the slurry subjected to ball milling into an evaporation pan, and placing the evaporation pan in an oven to be dried for 10 hours at the temperature of 60 ℃;
step 4, putting the dried powder into an alumina crucible, covering the alumina crucible, putting the alumina crucible into a muffle furnace for presintering to obtain presynthesized powder, setting the heating rate to be 2 ℃/min, the presintering temperature to be 850 ℃, keeping the temperature for 2 hours, and then naturally cooling along with the furnace;
step 5, putting the powder into a ball milling tank again for secondary ball milling, wherein agate round beads and absolute ethyl alcohol are still used as ball milling media in the process, the ball milling rotating speed is 400r/min, and the ball milling time is 11 hours;
step 6, pouring the slurry subjected to ball milling into an evaporation pan, covering to prevent impurities from entering, and drying in an oven at 80 ℃ for 8 hours;
step 7, taking out the dried powder, placing the powder in a mortar for full grinding, then dropwise adding 6wt% of PVA for granulation until the mixture is uniform, then sieving the mixture through a 100-mesh sieve, and bagging the mixture for later use;
step 8, weighing 0.25g of the powder, filling the powder into a cylindrical die with the diameter of 10mm, and performing prepressing molding on a powder tablet press;
step 9, putting the pre-pressed and molded green body into a butyronitrile glove, vacuumizing, and then putting into a cold isostatic press, and keeping the pressure for 1min under the condition of 200MPa to obtain a compact green body;
and step 10, placing the green body in a muffle furnace for binder removal, preserving heat for 10 hours at 500 ℃, then starting sintering, keeping the temperature for 4 hours at the temperature rising rate of 3 ℃/min and the sintering temperature of 1130 ℃, and then naturally cooling along with the furnace. It should be noted that, because Bi and Na are volatile elements, the ceramic green body needs to be covered with the powder during sintering to reduce volatilization;
step 11, grinding and polishing the sintered ceramic samples on 250-mesh, 800-mesh and 2000-mesh sandpaper respectively;
step 12, coating silver on the upper surface and the lower surface of the sample, and then putting the sample into a muffle furnace for heat preservation at 650 ℃ for 20min for testing the dielectric property; sputtering a Pt electrode on the surface of the sample by using a magnetron sputtering instrument for testing the electric hysteresis loop; other properties were obtained by directly using a sample sintered into porcelain.
Example 2
The chemical composition of the sodium bismuth titanate-based dielectric ceramic capacitor with high energy density provided in this embodiment is 0.92 (0.6 BNT-0.4 SBT) -0.08LMT, and the specific preparation process is as follows:
step 1, selecting Bi with purity higher than 99% from Alfa Aesar manufacturer 2 O 3 ,Na 2 CO 3 ,La 2 O 3 ,SrCO 3 MgO and TiO 2
Step 2, calculating the mass of the raw materials to be weighed according to the stoichiometric ratio, then weighing the 6 raw materials by using an electronic balance, placing the raw materials in a 50mL polytetrafluoroethylene ball milling tank, adding 30g of agate round beads and 25mL of absolute ethyl alcohol as ball milling media, wherein the ball milling speed is 450r/min, and the ball milling time is 10 hours;
step 3, pouring the slurry subjected to ball milling into an evaporation pan, and placing the evaporation pan in an oven to be dried for 10 hours at the temperature of 60 ℃;
step 4, putting the dried powder into an alumina crucible, covering the alumina crucible, putting the alumina crucible into a muffle furnace for presintering to obtain presynthesized powder, setting the heating rate to be 2 ℃/min, the presintering temperature to be 880 ℃, keeping the temperature for 3 hours, and then naturally cooling along with the furnace;
step 5, putting the powder into a ball milling tank again for secondary ball milling, wherein agate round beads and absolute ethyl alcohol are still used as ball milling media in the process, the ball milling speed is 450r/min, and the ball milling time is 10 hours;
step 6, pouring the slurry subjected to ball milling into an evaporating dish, covering to prevent impurities from entering, and drying for 8 hours at 80 ℃ in a drying oven;
step 7, taking out the dried powder, putting the powder into a mortar for full grinding, then dropwise adding 6wt% of PVA for granulation till the powder is uniform, then sieving the powder by a 100-mesh sieve, and bagging the powder for later use;
step 8, weighing 0.25g of the powder, filling the powder into a cylindrical die with the diameter of 10mm, and performing prepressing molding on a powder tablet press;
step 9, putting the pre-pressed and molded green body into a butyronitrile glove, vacuumizing, and then putting into a cold isostatic press, and keeping the pressure for 3min under the condition of 230MPa to obtain a compact green body;
and step 10, placing the green body in a muffle furnace for binder removal, preserving heat for 8 hours at 600 ℃, then starting sintering, preserving heat for 3 hours at the temperature rise rate of 3 ℃/min and the sintering temperature of 1150 ℃, and then naturally cooling along with the furnace. It should be noted that since Bi and Na are volatile elements, the ceramic green body needs to be covered with the powder thereof during sintering to reduce volatilization;
step 11, grinding and polishing the sintered ceramic samples on 250-mesh, 800-mesh and 2000-mesh sandpaper respectively;
step 12, coating silver on the upper surface and the lower surface of the sample, and then putting the sample into a muffle furnace for heat preservation at 650 ℃ for 20min for testing the dielectric property; sputtering a Pt electrode on the surface of the sample by using a magnetron sputtering instrument for testing the electric hysteresis loop; other properties were obtained by directly using a sample sintered into porcelain.
Example 3
The chemical composition of the sodium bismuth titanate-based dielectric ceramic capacitor with high energy density provided by the embodiment is 0.88 (0.6 BNT-0.4 SBT) -0.12LMT, and the specific preparation flow is as follows:
step 1, selecting Bi with the purity higher than 99% from Alfa Aesar manufacturers 2 O 3 ,Na 2 CO 3 ,La 2 O 3 ,SrCO 3 MgO and TiO 2
Step 2, calculating the mass of the raw materials to be weighed according to the stoichiometric ratio, then weighing the 6 raw materials by using an electronic balance, placing the raw materials in a 50mL polytetrafluoroethylene ball milling tank, adding 30g of agate round beads and 25mL of absolute ethyl alcohol as ball milling media, wherein the ball milling speed is 430r/min, and the ball milling time is 12 hours;
step 3, pouring the slurry subjected to ball milling into an evaporation pan, and placing the evaporation pan in an oven to be dried for 10 hours at the temperature of 60 ℃;
step 4, putting the dried powder into an alumina crucible, covering the alumina crucible, putting the alumina crucible into a muffle furnace for presintering to obtain presynthesized powder, setting the temperature rise rate to be 2 ℃/min, the presintering temperature to be 870 ℃, keeping the temperature for 4 hours, and then naturally cooling along with the furnace;
step 5, putting the powder into a ball milling tank again for secondary ball milling, wherein agate round beads and absolute ethyl alcohol are still used as ball milling media in the process, the ball milling rotating speed is 430r/min, and the ball milling time is 12 hours;
step 6, pouring the slurry subjected to ball milling into an evaporation pan, covering to prevent impurities from entering, and drying in an oven at 80 ℃ for 8 hours;
step 7, taking out the dried powder, placing the powder in a mortar for full grinding, then dropwise adding 6wt% of PVA for granulation until the mixture is uniform, then sieving the mixture through a 100-mesh sieve, and bagging the mixture for later use;
step 8, weighing 0.25g of the powder, filling the powder into a cylindrical die with the diameter of 10mm, and performing prepressing molding on a powder tablet press;
step 9, putting the pre-pressed and molded green body into a butyronitrile glove, vacuumizing, and then putting into a cold isostatic press, and keeping the pressure for 2min under the condition of 220MPa to obtain a compact green body;
and step 10, placing the green body in a muffle furnace for binder removal, preserving heat at 550 ℃ for 5h, then starting sintering, keeping the temperature for 2h at the heating rate of 3 ℃/min and the sintering temperature of 1140 ℃, and then naturally cooling along with the furnace. It should be noted that since Bi and Na are volatile elements, the ceramic green body needs to be covered with the powder thereof during sintering to reduce volatilization;
step 11, grinding and polishing the sintered ceramic samples on 250-mesh, 800-mesh and 2000-mesh sandpaper respectively;
step 12, coating silver on the upper surface and the lower surface of the sample, and then placing the sample into a muffle furnace for heat preservation at 650 ℃ for 20min for testing dielectric property; sputtering a Pt electrode on the surface of the sample by using a magnetron sputtering instrument for testing the electric hysteresis loop; other properties were obtained by directly using a sample sintered into porcelain.
As can be seen from FIG. 1, the BNT-based ceramics prepared according to the invention have perovskite structures, the comparative examples and the ceramics prepared in all the examples have perovskite structures, which shows that LaMg has 0.5 Ti 0.5 O 3 The doping does not cause a change in the macrostructure.
As can be seen from FIGS. 2 (a) to 2 (d), the ceramics prepared in the comparative example and all of the examples exhibited a dense microstructure with average grain sizes of 1.07 μm,1.05 μm,0.96 μm and 0.38 μm, respectively, indicating that with LaMg 0.5 Ti 0.5 O 3 The doping amount of (2) is increased and the grain size is gradually reduced, which is favorable for the improvement of the breakdown electric field.
FIGS. 3 (a) to 3 (d) are dielectric temperature spectra of ceramics prepared in the comparative example and all examples, respectively, and the test temperature ranges are-100 to 420 deg.C, and the test frequency is dividedRespectively 0.1kHz,1kHz,10kHz,100kHz and 1000kHz. As can be seen from fig. 3 (a) -3 (d), all the components have two dielectric abnormal peaks, the dielectric abnormal peaks at low temperatures exhibit frequency dispersion characteristics, which are characteristic of typical relaxants, and the dielectric constants exhibit good temperature stability. With LaMg 0.5 Ti 0.5 O 3 The doping amount of (a) is increased, the dielectric constant is gradually reduced, two dielectric peaks move towards the low temperature direction, and for the ceramic sample prepared in example 2, the dielectric constant is maintained in the range of-37.9 ℃ to 318.2 ℃, which is beneficial to obtaining excellent room temperature performance.
Fig. 4 is a hysteresis loop of the ceramics prepared in the comparative example and all examples at room temperature. As can be seen from FIG. 4, the comparative example prepared ceramic had a relatively large hysteresis loop and a storage energy density of 3.65J/cm at a breakdown field strength of 260kV/cm 3 The energy storage efficiency is 86.46%; with LaMg 0.5 Ti 0.5 O 3 The amount of doping of (a) was increased, the hysteresis loop became gradually elongated and the breakdown electric field was gradually increased, and for the ceramic sample prepared in example 2, the maximum polarization was 44.14. Mu.C/cm at a breakdown field strength of 390kV/cm 2 The remanent polarization is 1.15 mu C/cm 2 The obtained energy storage density is 6.79J/cm 3 The energy storage efficiency is 93%, and excellent energy storage performance is obtained under a lower electric field.
From the results in fig. 4, it can be seen that the sample prepared in example 2 performed best, and therefore the following analysis was developed specifically for example 2.
Fig. 5 is a temperature swing hysteresis loop for the x =0.08 ceramic composition made in example 2. As can be seen from fig. 5, the temperature-changing hysteresis loops of the ceramic composition exhibit a series of elongated shapes. Within the test range (-50-200 ℃), the maximum polarization was 34.91. Mu.C/cm at an electric field strength of 260kV/cm 2 The energy storage density corresponding to the density is more than 3.73J/cm 3 The energy storage efficiency is higher than 88%, and the temperature stability is excellent.
Fig. 6 is a frequency conversion hysteresis loop for the x =0.08 ceramic composition prepared in example 2. As can be seen from FIG. 6, the frequency conversion hysteresis loop of the ceramic composition appearsA series of elongated shapes. In the test range (2 Hz-100 Hz), when the electric field strength is 260kV/cm, the energy storage density corresponding to the electric field strength is more than 3.87J/cm 3 The energy storage efficiency is higher than 93%, and the frequency stability is excellent.
Fig. 7 is a fatigue hysteresis loop for the x =0.08 ceramic composition prepared in example 2. As can be seen in FIG. 7, the fatigue hysteresis loops of the ceramic composition exhibit a series of elongated shapes, undergoing 10 5 After the secondary circulation, the anti-fatigue property is still excellent.

Claims (10)

1. A sodium bismuth titanate-based dielectric ceramic capacitor with high energy density is characterized by comprising the following chemical components:
(1-x)(0.6Bi 0.5 Na 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 )-xLaMg 0.5 Ti 0.5 O 3 wherein x represents LaMg 0.5 Ti 0.5 O 3 The value of x is in the range of 0.04-0.12.
2. The sodium bismuth titanate-based dielectric ceramic capacitor with high energy density as claimed in claim 1, wherein x is 0.08.
3. The method for preparing a high energy density sodium bismuth titanate-based dielectric ceramic capacitor as claimed in claim 1, comprising the steps of:
uniformly mixing the raw material powder to obtain initial powder;
presintering the initial powder at 850-880 ℃ for 2-4h to obtain presynthesized ceramic powder;
uniformly mixing the pre-synthesized ceramic powder, granulating, pre-pressing and forming, and carrying out cold isostatic pressing to obtain a ceramic green body;
and (3) carrying out binder removal on the ceramic green body, then sintering for 2-4h at 1130-1150 ℃, and naturally cooling to room temperature along with the furnace to obtain the high-energy-density sodium bismuth titanate-based dielectric ceramic capacitor.
4. Root of herbaceous plantThe method of claim 3, wherein the raw material powder comprises Bi 2 O 3 Powder, na 2 CO 3 Powder, la 2 O 3 Powder, srCO 3 Powder, mgO powder and TiO 2 And (3) powder.
5. The preparation method of the high-energy-density sodium bismuth titanate-based dielectric ceramic capacitor as claimed in claim 4, wherein the raw material powder is uniformly mixed by ball milling at a rotation speed of 400-450r/min for 10-12h.
6. The preparation method of the high-energy-density sodium bismuth titanate-based dielectric ceramic capacitor as claimed in claim 3, wherein the pre-synthesized ceramic powder is uniformly mixed by ball milling at a rotation speed of 400-450r/min for 10-12h.
7. The method of claim 3, wherein the granulation is carried out using a polyvinyl alcohol solution as a binder.
8. The method of claim 7, wherein the ceramic green body is subjected to binder removal at a temperature of 500-600 ℃ for 5-10h.
9. The method of claim 3, wherein the pre-press molding pressure is controlled to 2-4MPa.
10. The method of claim 3, wherein the cold isostatic pressing is performed at a pressure of 200-230MPa for a dwell time of 1-3min.
CN202211542365.8A 2022-12-02 2022-12-02 High-energy-density sodium bismuth titanate-based dielectric ceramic capacitor and preparation method thereof Pending CN115881430A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116693285A (en) * 2023-05-22 2023-09-05 南昌航空大学 Super-cis-electric-phase sodium bismuth titanate-based relaxation energy storage ceramic material and preparation method thereof
CN116751051A (en) * 2023-05-30 2023-09-15 西安交通大学 Bismuth sodium titanate-based ceramic capacitor with high energy storage performance and preparation method thereof
CN116854464A (en) * 2023-07-07 2023-10-10 石河子大学 Ferroelectric composite energy storage ceramic material and preparation method thereof
CN117342869A (en) * 2023-09-21 2024-01-05 京瓷高压(西安)科技有限公司 Low-lead capacitor ceramic capable of tolerating high Leng Gao heat and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116693285A (en) * 2023-05-22 2023-09-05 南昌航空大学 Super-cis-electric-phase sodium bismuth titanate-based relaxation energy storage ceramic material and preparation method thereof
CN116751051A (en) * 2023-05-30 2023-09-15 西安交通大学 Bismuth sodium titanate-based ceramic capacitor with high energy storage performance and preparation method thereof
CN116854464A (en) * 2023-07-07 2023-10-10 石河子大学 Ferroelectric composite energy storage ceramic material and preparation method thereof
CN116854464B (en) * 2023-07-07 2024-04-16 石河子大学 Ferroelectric composite energy storage ceramic material and preparation method thereof
CN117342869A (en) * 2023-09-21 2024-01-05 京瓷高压(西安)科技有限公司 Low-lead capacitor ceramic capable of tolerating high Leng Gao heat and preparation method thereof

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