CN114671681B - Barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency and preparation method thereof - Google Patents

Barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency and preparation method thereof Download PDF

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CN114671681B
CN114671681B CN202210373275.4A CN202210373275A CN114671681B CN 114671681 B CN114671681 B CN 114671681B CN 202210373275 A CN202210373275 A CN 202210373275A CN 114671681 B CN114671681 B CN 114671681B
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刘辉
孙正
罗华杰
陈骏
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University of Science and Technology Beijing USTB
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Abstract

The invention provides a barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency and a preparation method thereof, belonging to the technical field of dielectric medium energy storage ceramic materials; the chemical composition of the material is Bi x Ba 1‑3x/2 TiO 3 (x is more than or equal to 0.08 and less than or equal to 0.18). The method comprises the following steps: in BaTiO 3 A site of (A) introduces Bi 3+ Then synthesized by a solid-phase reaction method. The energy storage density of the barium titanate-based relaxor ferroelectric ceramic material prepared by the invention can reach 6.48J/cm 3 The energy storage efficiency can be stabilized above 92%, and can reach 94.6% under an electric field of 480 kV/cm. In addition, the preparation method is simple, low in cost, environment-friendly and capable of realizing large-scale production.

Description

Barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency and preparation method thereof
Technical Field
The invention relates to the field of dielectric energy storage ceramic materials, in particular to a barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency and a preparation method thereof.
Background
In recent years, energy storage ceramic capacitors have been widely used in pulse power electronic systems such as communications, medical treatment, military affairs, etc. with the advantages of high electric field resistance, high power density, etc. At present, the most widely used energy storage ceramic capacitor belongs to a lead-based capacitor, but with the requirement of environmental protection and the advance of sustainable development strategy, the development of lead-free ceramic capacitors has gradually become a necessary trend. Compared with lead-based energy storage ceramic, the biggest problem restricting the development of lead-free energy storage ceramic is that the energy storage density is low, and the development trend of miniaturization and integration of pulse power system components is difficult to comply. Researches show that materials with high energy storage density generally have the characteristics of high electric field resistance, low dielectric loss, high dielectric constant and the like.
Among the lead-free functional ceramics, barium titanate ceramics have the advantages of large dielectric constant, low dielectric loss and the like, and are widely applied to the field of electronic components such as multilayer ceramic capacitors and the like at present. However, barium titanate ceramic as an energy storage material has the defects of poor temperature stability, low breakdown field strength, low energy storage efficiency and the like, and the application of the barium titanate ceramic in the energy storage material is limited. In view of the above, barium titanate-based relaxor ferroelectrics are synthesized mainly by doping modification, cladding modification, and the like at the present stage, but no energy storage material having high energy storage density, high power density, and high efficiency has been found yet.
Disclosure of Invention
The invention aims to provide a barium titanate-based relaxor ferroelectric ceramic material and a preparation method thereof, wherein the barium titanate-based relaxor ferroelectric ceramic material has high energy storage density, high power density and high efficiency.
In order to solve the technical problems, the invention provides the following technical scheme:
in a first aspect, there is provided a barium titanate-based relaxor ferroelectric ceramic material having a chemical composition of Bi and exhibiting high energy storage density, high power density and high efficiency x Ba 1-3x/2 TiO 3 (0.08≤x≤0.18)。
Preferably, 0.10. Ltoreq. X.ltoreq.0.16, x being, in particular, 0.10, 0.12, 0.13, 0.14, 0.15, 0.16, for example.
More preferably, x =0.12.
Under the preferable x scheme, the energy storage density can reach 6.48J/cm 3 The energy storage efficiency can be stabilized to be more than 92%, and can reach 94.6% under an electric field of 480 kV/cm. This is mainly because of Bi 3+ By substitution modification of BaTiO 3 The macroscopic electric domain is changed into the polar nano domain, and the relaxivity is enhanced. The crystal grain size of the component is smaller, the density is higher, and the component has higher breakdown field strength.
In a second aspect, there is provided a method for preparing the barium titanate-based relaxor ferroelectric ceramic material of the first aspectThe method comprises the following steps: in BaTiO 3 A site of (A) introduces Bi 3+ Then synthesized by a solid-phase reaction method.
Wherein, preferably, the following steps are specifically adopted:
s1, according to Bi x Ba 1-3x/2 TiO 3 Stoichiometric weighing of Bi 2 O 3 、BaCO 3 、TiO 2 Mixing the powder with ethanol, performing ball milling, drying, grinding, primary calcining and cooling;
s2, dropwise adding a binder into the sample obtained after the calcination of the S1 for granulation, and then sintering;
and S3, polishing the ceramic wafer obtained by sintering the S2, coating silver paste on the upper surface and the lower surface, then carrying out secondary calcination, and cooling to obtain the barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency.
Wherein, the ball milling time in S1 is 12-24h.
The dosage of the ethanol in the S1 can be freely selected according to the volume of the adopted container and the grinding uniformity, so long as the uniform grinding is facilitated, and the ethanol can be gradually evaporated in the subsequent treatment process.
Wherein, preferably, the conditions of the primary calcination in S1 include: the temperature is 600-900 ℃ and the time is 1-3h.
Wherein, preferably, the binder in S2 is one of PVA and PVB.
Preferably, the mass ratio of the binder to the sample obtained after the calcination of S1 is 1.
Wherein, preferably, the sintering conditions in S2 include: the temperature is 1100-1300 ℃ and the time is 1-3h.
Wherein, preferably, the conditions of the secondary calcination in S3 include: the temperature is 500-800 ℃ and the time is 0.5-3h.
The technical scheme of the invention has the following beneficial effects:
through substitution modification, the barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency is invented, namelyBi x Ba 1-3x/2 TiO 3 A relaxor ferroelectric ceramic. The energy storage density reaches 6.48J/cm 3 The energy storage efficiency can be stabilized above 92%, and can reach 94.6% under an electric field of 480kV/cm, which exceeds the performance of most of the reported energy storage ceramics. In addition, the material has low cost, simple preparation method, environmental friendliness and long service life, can be produced in large scale, and is expected to replace other energy storage ceramic materials. No Bi is currently available in the prior art x Ba 1-3x/2 TiO 3 Report on relaxor ferroelectric ceramics.
The invention has high energy storage density, high power density and high energy storage efficiency, and can be widely applied to pulse power electronic systems such as mobile communication, medical treatment and health, national defense and military and the like. The preparation method is simple, low in cost, suitable for large-scale production and beneficial to promoting relevant application of the preparation method.
Drawings
FIG. 1 is an SEM photograph of a barium titanate-based relaxor ferroelectric ceramic obtained in example 1;
FIG. 2 is a ferroelectric hysteresis loop of the barium titanate-based relaxor ferroelectric ceramic obtained in example 1;
fig. 3 is a graph showing the change in energy storage characteristics with electric field strength of the barium titanate-based relaxor ferroelectric ceramic obtained in example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Example 1:
preparation of Bi by the invention 0.12 Ba 0.82 TiO 3 . Weighing 1.8638 g of Bi according to the chemical dose ratio 2 O 3 10.7877 grams of BaCO 3 5.3244 g TiO 2 And poured into a ball milling tank, added with ethanol and ball milled for 24 hours. And (3) drying and grinding the ball-milled sample in sequence, and then putting the ball-milled sample into a muffle furnace to set the temperature at 850 ℃ for calcining for 2 hours. After cooling, the sample is poured into a mortar, a proper amount of PVA binder (the mass ratio of the binder to the sample is 1: 10) is dripped into the mortar for grinding for 1 hour, the mixture is uniformly ground, and the PVA binder is poured into the mortar for grinding for 1 hour
Figure SMS_1
The die is pressed into tablets, and then the tablets are placed into a muffle furnace to be sintered for 2 hours at the temperature of 1160 ℃. After cooling, the ceramic wafer is polished to 0.4mm in thickness, silver paste is brushed on the upper surface and the lower surface of the ceramic wafer, and then the ceramic wafer is calcined for 1 hour at 550 ℃. After cooling, the barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency can be obtained.
Fig. 1 is an SEM picture of the barium titanate-based relaxor ferroelectric ceramic obtained in this example, and it can be seen that the ceramic has a grain size of about 1 μm and a high degree of compactness.
FIG. 2 is a unipolar ferroelectric hysteresis loop at room temperature of the barium titanate-based relaxor ferroelectric ceramic prepared in this example, and it can be seen from the figure that the hysteresis loop is elongated and the maximum electric field strength can reach 550kV/cm.
FIG. 3 is a graph showing the energy storage characteristics of the barium titanate-based relaxor ferroelectric ceramic prepared in this example as a function of the electric field intensity, and it can be seen from the graph that the energy storage density of the ceramic can reach 6.48J/cm under the electric field of 550kV/cm 3 (ii) a The energy storage efficiency can be stabilized above 92%, and can reach 94.6% under an electric field of 480kV/cm, and the data exceeds most of the previously reported energy storage ceramic materials.
Example 2:
the invention is utilized to prepare Bi 0.14 Ba 0.79 TiO 3 . Weighing 2.1745 g of Bi according to the chemical dose ratio 2 O 3 10.3931 g of BaCO 3 5.3244 g TiO 2 Pouring into a ball milling tank, adding ethanol, and ball milling for 24h. And (3) drying and grinding the ball-milled sample in sequence, and then putting the ball-milled sample into a muffle furnace to set the temperature at 850 ℃ for calcining for 2 hours. After cooling, the sample was poured into a mortar, a proper amount of PVA binder (the amount ratio of the binder to the sample was the same as in example 1) was added dropwise, the mixture was uniformly ground (the grinding time was the same as in example 1), and the mixture was poured into a mortar
Figure SMS_2
In the mould, pressing into tablets, then putting into a muffle furnace for setting the temperatureSintering at 1140 deg.C for 2h. After cooling, the thickness of the ceramic wafer is polished to 0.4mm, silver paste is brushed on the upper surface and the lower surface of the ceramic wafer, and then the ceramic wafer is calcined at 550 ℃ for 1h. After cooling, the barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency can be obtained.
Tests prove that the barium titanate-based relaxor ferroelectric ceramic prepared in the embodiment has the energy storage density of 5.56J/cm under the electric field of 480kV/cm 3 And the energy storage efficiency reaches 87.82 percent.
Example 3:
bi preparation by the invention 0.16 Ba 0.76 TiO 3 . Weighing 2.4851 g of Bi according to the chemical dose ratio 2 O 3 9.9984 grams of BaCO 3 5.3244 g TiO 2 Pouring into a ball milling tank, adding ethanol, and ball milling for 24h. And (3) drying and grinding the ball-milled sample in sequence, and then putting the ball-milled sample into a muffle furnace to set the temperature at 850 ℃ for calcining for 2h. After cooling, the sample was poured into a mortar, an appropriate amount of PVA binder (the amount of binder to sample was the same as in example 1) was added dropwise, the mixture was ground uniformly (the grinding time was the same as in example 1), and the mixture was poured into a mortar
Figure SMS_3
The die of (2) was pressed into a tablet, which was then sintered in a muffle furnace set at a temperature of 1120 ℃ for 2 hours. After cooling, the ceramic wafer is polished to 0.4mm in thickness, silver paste is brushed on the upper surface and the lower surface of the ceramic wafer, and then the ceramic wafer is calcined for 1 hour at 550 ℃. After cooling, the barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency can be obtained.
Tests prove that the barium titanate-based relaxor ferroelectric ceramic prepared from the components has the energy storage density of 5.91J/cm under the electric field of 540kV/cm 3 And the energy storage efficiency reaches 90.10 percent.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (3)

1. AThe barium titanate-based relaxor ferroelectric ceramic material with high energy storage density, high power density and high efficiency is characterized in that the chemical composition of the barium titanate-based relaxor ferroelectric ceramic material is Bi x Ba 1-3x/2 TiO 3 Wherein x =0.12;
the preparation method of the barium titanate-based relaxor ferroelectric ceramic material comprises the following steps:
s1, according to Bi x Ba 1-3x/2 TiO 3 Stoichiometric weighing of Bi 2 O 3 、BaCO 3 、TiO 2 Mixing with ethanol, ball milling, drying, grinding and primary calcining; the conditions of the primary calcination include: the temperature is 850 ℃, and the time is 2h;
s2, dropwise adding a binder into the sample obtained after the calcination of the S1 for granulation, and then sintering; the sintering conditions include: the temperature is 1160 ℃, and the time is 2h;
s3, polishing the ceramic wafer obtained by sintering the S2, coating silver paste on the upper surface and the lower surface, and then performing secondary calcination; the conditions of the secondary calcination include: the temperature is 550 ℃ and the time is 1h.
2. The barium titanate-based relaxor ferroelectric ceramic material of claim 1, wherein the ball milling time in S1 is 12 to 24 hours.
3. The barium titanate-based relaxor ferroelectric ceramic material of claim 1, wherein the binder in S2 is PVA or PVB.
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