CN116444267A - High-temperature strong-field high-dielectric low-loss energy storage ceramic and preparation method thereof - Google Patents

High-temperature strong-field high-dielectric low-loss energy storage ceramic and preparation method thereof Download PDF

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CN116444267A
CN116444267A CN202310506422.5A CN202310506422A CN116444267A CN 116444267 A CN116444267 A CN 116444267A CN 202310506422 A CN202310506422 A CN 202310506422A CN 116444267 A CN116444267 A CN 116444267A
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energy storage
temperature
dielectric
storage ceramic
ball milling
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吴隆文
兰贵天
赵莉华
贾申利
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Sichuan University
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Abstract

The invention discloses a high-temperature strong-field high-dielectric low-loss energy-storage ceramic and a preparation method thereof, wherein the energy-storage ceramic comprises the following components in percentage by weight: (1-y-z) [ (1-x) BaTiO 3 ‑xBiMeO 3 ]+ym+ zQ, wherein Me represents a single trivalent metal cation or a combination of multiple metal cations that are on average trivalent; m represents a linear dielectric; q represents an antiferroelectric body; x represents BiMeO 3 Mole fraction of (a); y represents the mole fraction of the linear dielectric M; z represents the molar fraction of antiferroelectric Q.

Description

High-temperature strong-field high-dielectric low-loss energy storage ceramic and preparation method thereof
Technical Field
The invention relates to the technical field of ceramic materials, in particular to high-temperature strong-field high-dielectric low-loss energy storage ceramic and a preparation method thereof.
Background
The power electronics technology has an indispensable role as a core technology for converting and controlling electric energy in an electric power system. The energy storage dielectric capacitor is used as an essential element in power electronics technology, and is widely applied to power converters such as ac-dc inverters, ac-dc rectifiers, dc buck-boost converters and the like. In the technical field of power electronics, an energy storage dielectric capacitor plays key roles of absorbing ripple current, balancing instantaneous power, inhibiting peak voltage and the like. With the advent of third generation semiconductor technology and the rising of industries such as micro-grids, electric automobiles, all-electric airplanes and the like, power converters are developed towards high power density, high temperature and high voltage, and have higher performance requirements on energy storage dielectric capacitors, and the core for determining the performance of the energy storage capacitors is the energy storage dielectric material.
Among the energy storage dielectric materials, the relaxation ferroelectric energy storage ceramic material obtained by doping and modifying the ferroelectric ceramic has an elongated electric hysteresis loop, so that the relaxation ferroelectric energy storage ceramic material has the advantages of higher energy storage density and smaller loss. BaTiO 3 -BiMeO 3 The basic energy storage ceramic has extremely slender electric hysteresis loop and becomes a research hot spot in recent years. For example, "patent publication No.: CN108623300a, name: barium titanate-bismuth zincate niobate based leadless relaxor ferroelectric energy storage ceramic and its preparation method, which develops 0.9BaTiO 3 -0.1Bi[Zn 2/3 (Nb 0.9 Ta 0.1 ) 1/3 ]O 3 Relaxation ferroelectric energy storage ceramic, single-layer ceramic energy storage density reaches 7.81J/cm 3 The efficiency is more than 95%. And the patent publication number is as follows: CN110511018A, name: a Chinese patent invention of high energy storage density ceramic capacitor dielectric and its preparation method, which develops 0.375BiFeO 3 -0.625[0.85BaTiO 3 -0.15Bi(Sn 0.5 Zn 0.5 )O 3 ]Relaxation ferroelectric ceramic with energy storage density up to 3.23J/cm 3 The energy storage efficiency reaches 84 percent.
However, baTiO currently being developed 3 -BiMeO 3 The base energy storage ceramic has higher dielectric constant and lower loss under low temperature and weak electric field. However, as the electric field strength and temperature are increased, the dielectric constant is greatly reduced, and the loss is greatly increased, resulting in a great reduction in energy storage characteristics. Thus, baTiO, which has been developed so far 3 -BiMeO 3 The basic energy storage ceramic still cannot meet the requirement that the power converter is towardsHigh power density, high temperature, high voltage.
Therefore, there is an urgent need to develop BaTiO having a high dielectric constant and a low loss under a high-temperature strong electric field 3 -BiMeO 3 And (3) a base energy storage ceramic material.
Disclosure of Invention
Aiming at the problems, the invention aims to provide the energy storage ceramic with high temperature, strong field, high dielectric constant and low loss and the preparation method thereof, and the technical scheme adopted by the invention is as follows:
an energy storage ceramic with high temperature, strong field, high dielectric constant and low loss, wherein the energy storage ceramic has the following component expression:
(1-y-z)[(1-x)BaTiO 3 -xBiMeO 3 ]+yM+zQ (1)
wherein Me represents a single trivalent metal cation or a combination of multiple metal cations of average trivalent, such as Mg, ti, zn, nb, ta, sc, etc.; m represents a linear dielectric; q represents an antiferroelectric body; x represents BiMeO 3 The molar fraction of (2) is [0.01,0.40 ]]The method comprises the steps of carrying out a first treatment on the surface of the y represents the mole fraction of the linear dielectric M, which is 0 or [0.05,0.4]The method comprises the steps of carrying out a first treatment on the surface of the z represents the molar fraction of the antiferroelectric Q, which is 0 or [0.05,0.4]The method comprises the steps of carrying out a first treatment on the surface of the The mole fractions of the linear dielectric M and the antiferroelectric Q are not simultaneously taken to be 0.
Preferably, the linear dielectric M is SrTiO 3 、SrZrO 3 、CaTiO 3 、CaZrO 3 One of them.
Further, the antiferroelectric body Q adopts NaNbO 3 、AgNbO 3 One of them.
Further, when the molar fraction of the antiferroelectric body Q is 0, the composition expression of the energy storage ceramic is as follows:
(1-y)[(1-x)BaTiO 3 -xBiZn 2/3 (Nb 0.6 Ta 0.4 ) 1/3 O 3 ]+yCaZrO 3
wherein y is more than or equal to 0.05 and less than or equal to 0.4, and x is more than or equal to 0.01 and less than or equal to 0.4.
Further, when the mole fraction of the linear dielectric M takes a value of 0, the composition expression of the energy storage ceramic is as follows:
(1-z)[(1-x)BaTiO 3 -xBiScO 3 ]+zNaNbO 3
wherein, z is more than or equal to 0.05 and less than or equal to 0.4, and x is more than or equal to 0.01 and less than or equal to 0.4.
A preparation method of high-temperature strong-field high-dielectric low-loss energy storage ceramic comprises the following steps:
in BaCO 3 、TiO 2 、Bi 2 O 3 、ZnO、Nb 2 O 5 、Ta 2 O 5 、CaCO 3 And ZrO(s) 2 The preparation method comprises the following steps of (1) preparing raw materials according to the stoichiometric ratio of a chemical formula: ball milling, primary drying, presintering, secondary ball milling, secondary drying, granulating, tabletting, glue discharging and sintering, silver coating/metal spraying and testing;
in the steps of primary ball milling and secondary ball milling, zrO with the diameter of 1-10 mm is selected 2 Grinding the ball; adding a solvent medium in the steps of primary ball milling and secondary ball milling; the raw material, the medium of the solvent and ZrO 2 The mass ratio of the abrasive of the ball is 1:10 to 15:10 to 15 percent; the time of the primary ball milling is 16-24 hours; the time of the secondary ball milling is 6-12 hours; the ZrO 2 Ball milling is carried out in one direction, and the rotating speed is 250-350 r/min;
the temperature of the primary drying and the secondary drying is 60-70 ℃ and the drying time is 6-8 h;
in the presintering process, the temperature rising rate is 3 ℃/min, the presintering temperature is 850-1050 ℃, the heat preservation time is 2-4 h, and natural cooling is adopted;
the granulating is added with a binder; the adhesive takes absolute ethyl alcohol as a solvent and is dissolved with polyvinyl butyral with the mass percent of 3-10%; the mass ratio of the binder to the ceramic powder after secondary drying is 10% -20%;
in the glue discharging sintering, the heating rate is kept at 3 ℃/min, the glue discharging temperature is 500-700 ℃, and the heat preservation time is 2-4 h; sintering at 1150-1250 deg.c for 2-4 hr and naturally cooling;
in the silver coating/metal spraying process, the silver coating process is as follows: uniformly coating silver paste on the surface of the sintered ceramic sample or uniformly coating by adopting a screen printer, and treating for 10min at 500-700 ℃ to form a silver electrode; the metal spraying process is as follows: and sputtering and spraying gold on the two sides of the ceramic sample for 300-400 s by adopting a mask plate with a round hole diameter of 2-6 mm, and forming a gold electrode.
Preferably, the solvent is ultrapure water or absolute ethanol or toluene.
Further, in the tabletting, the diameter of the die is 5-10 mm, the pressure applied to the die is 2MPa, and the thickness of the ceramic blank after tabletting is 0.2-1 mm.
Further, the weighing error of the raw materials is not more than 0.1% of the total mass.
Compared with the prior art, the invention has the following beneficial effects:
the invention is realized by the method of preparing BaTiO 3 -BiMeO 3 The energy storage ceramic material with high dielectric constant and low dielectric loss under high-temperature strong electric field is obtained by doping and modifying the base energy storage ceramic. The invention is realized by selecting proper doping material (CaTiO 3 、CaZrO 3 、NaNbO 3 、AgNbO 3 Etc.), suitable x, y, z values, and suitable process conditions, the BaTiO may be such that 3 -BiMeO 3 The base energy storage ceramic has high dielectric constant and low dielectric loss under a high-temperature strong electric field so as to meet the development requirements of the power converter towards the high power density, high temperature and high voltage directions.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, the drawings to be used in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and should not be considered as limiting the scope of protection, and other related drawings may be obtained according to these drawings without the need of inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the relationship between dielectric constant and efficiency and electric field at 200℃for the energy storage ceramic of example 1.
FIG. 2 is a graph showing the relationship between dielectric constant and efficiency and temperature of the energy storage ceramic of example 1 under an electric field of 250 to 300 kV/cm.
FIG. 3 is a graph of the energy storage ceramic of example 2 and original 0.6BaTiO 3 -0.4BiScO 3 The bias characteristics of the components are compared to the graph.
FIG. 4 is the original 0.6BaTiO of example 3 3 -0.4Bi(Mg 1/2 Ti 1/2 )O 3 Dielectric constant versus temperature plot of the components.
FIG. 5 is a graph showing the relationship between dielectric constant and temperature of the energy storage ceramic in example 3.
FIG. 6 is a graph of the energy storage ceramic of example 3 and original 0.6BaTiO 3 -0.4Bi(Mg 1/2 Ti 1/2 )O 3 Comparison of the properties of the components at 200℃and high electric field.
FIG. 7 is a graph of the energy storage ceramic of example 3 and original 0.6BaTiO 3 -0.4Bi(Mg 1/2 Ti 1/2 )O 3 Comparison of the properties of the components at a temperature of 50℃and a high electric field.
FIG. 8 is a graph of the energy storage ceramic of example 3 and original 0.6BaTiO 3 -0.4Bi(Mg 1/2 Ti 1/2 )O 3 Comparison of the properties of the components at a temperature of 50℃and a low electric field.
Detailed Description
For the purposes, technical solutions and advantages of the present application, the present invention will be further described with reference to the accompanying drawings and examples, and embodiments of the present invention include, but are not limited to, the following examples. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
In this embodiment, the term "and/or" is merely an association relationship describing the association object, and indicates that three relationships may exist, for example, a and/or B may indicate: a exists alone, A and B exist together, and B exists alone.
The terms first and second and the like in the description and in the claims of the present embodiment are used for distinguishing between different objects and not for describing a particular sequential order of objects. For example, the first target object and the second target object, etc., are used to distinguish between different target objects, and are not used to describe a particular order of target objects.
In the embodiments of the present application, words such as "exemplary" or "such as" are used to mean serving as examples, illustrations, or descriptions. Any embodiment or design described herein as "exemplary" or "for example" should not be construed as preferred or advantageous over other embodiments or designs. Rather, the use of words such as "exemplary" or "such as" is intended to present related concepts in a concrete fashion.
In the description of the embodiments of the present application, unless otherwise indicated, the meaning of "a plurality" means two or more. For example, the plurality of processing units refers to two or more processing units; the plurality of systems means two or more systems.
Embodiment 1
The embodiment provides a high-temperature high-field high-dielectric low-loss energy-storage ceramic and a preparation method thereof, wherein the composition expression of the energy-storage ceramic is as follows: 0.9{0.8BaTiO 3 -0.2Bi[Zn 2/3 (Nb 0.6 Ta 0.4 ) 1/3 ]O 3 }+0.1CaZrO 3 The preparation method comprises the following specific steps:
weighing, ball milling for one time and presintering:
taking 10g of ceramic powder as an example, analytically pure BaCO was weighed according to the formula 3 、TiO 2 、Bi 2 O 3 、ZnO、Nb 2 O 5 、Ta 2 O 5 、CaCO 3 、ZrO 2 Raw materials. 150 g-200 g absolute ethyl alcohol and ZrO 2 150 g-200 g of grinding ball and the weighed raw materials are put into a ball milling tank for ball milling for one time, and one-way ball milling is carried out for 300-600 min; and then drying at 60-80 ℃ for 4-8 hours, and preserving heat at 800-1000 ℃ for 4-8 hours to burn in. ZrO (ZrO) 2 The diameter ratio of the grinding balls is 10mm:6mm:3mm = 1:3:6.
secondary ball milling, granulating, discharging glue and sintering:
re-sintering the pre-sintered powder150 g-200 g of absolute ethyl alcohol and ZrO at one time 2 Mixing 150 g-200 g of grinding balls, ball milling for 720min in a ball milling tank, heat preserving for 4-8 h at 60-80 ℃ for drying, granulating by adding PVB adhesive with the mass fraction of 5-10%, and tabletting for molding. Placing the mixture into a sintering furnace, firstly raising the temperature to 400-600 ℃ at 3 ℃/min, discharging glue for 240-480 min, then raising the temperature to 1150-1200 ℃ and preserving the heat for 240-480 min to sinter.
Polishing, metal spraying and testing:
polishing the sintered ceramic wafer to 0.15mm by using fine sand paper, flatly pasting the ceramic wafer on a mask plate with a round hole diameter of 3mm, and spraying gold on the two sides of the ceramic wafer in an ion sputtering instrument for 300-400 s to form a gold electrode, so as to prepare the wafer ceramic capacitor. The prepared ceramic capacitor was subjected to a direct-current bias hysteresis loop test, and the results are shown in fig. 1 and 2. The dielectric constant and the efficiency are obtained by calculating a tested direct-current bias hysteresis loop, and the calculating method comprises the following steps:
wherein P is polarization intensity, E is electric field intensity, ε 0 Is vacuum dielectric constant, W dis Discharge energy density, W cha Charge energy density.
In addition, FIG. 1 shows the dielectric constant of the ceramic at 200℃and 250kV/cm to 300kV/cm, and FIG. 2 shows the relationship between the dielectric constant, efficiency and temperature of the ceramic. It can be seen that 0.9{0.8BaTiO 3 -0.2Bi[Zn 2/3 (Nb 0.6 Ta 0.4 ) 1/3 ]O 3 }+0.1CaZrO 3 The dielectric constant of the ceramic is maintained to be more than 380, the charge and discharge efficiency is more than 95% when the electric field is 300kV/cm and the temperature is 200 ℃, and the specific performances are shown in the table 1.
Table 1 energy storage characteristics of the energy storage ceramic of example 1 under high temperature strong electric field
Example 2
The embodiment provides an energy storage ceramic with high temperature, strong field, high dielectric constant and low loss, and the composition expression is as follows: 0.8 (0.6 BaTiO) 3 -0.4BiScO 3 )+0.2NaNbO 3 . The dielectric constant of the material varies with the electric field under the same test conditions as shown in FIG. 3. Compared with 0.6BaTiO 3 -0.4BiScO 3 Original component, modified 0.8 (0.6 BaTiO) 3 -0.4BiScO 3 )+0.2NaNbO 3 The breakdown field intensity of the ceramic is obviously improved. The dielectric constant is higher than that of the original component under a strong electric field, and the bias characteristic is better than that of the original component, so that the method is suitable for application under higher field intensity. The storage density of the raw components under the test conditions is at most 2.0J/cm 3 The dielectric constant of the optimized ceramic component can reach 3.0J/cm 3 Is also significantly improved.
Example 3
The embodiment provides an energy storage ceramic with high temperature, strong field, high dielectric constant and low loss, and the composition expression is as follows: 0.8[0.6BaTiO ] 3 -0.4Bi(Mg 1/2 Ti 1/2 )O 3 ]+0.1SrTiO 3 +0.1AgNbO 3 . The dielectric constant and dielectric loss thereof with temperature under the same test conditions are shown in fig. 4 to 5. Compared with 0.6BaTiO 3 -0.4Bi(Mg 1/2 Ti 1/2 )O 3 The dielectric loss of the ceramic is obviously reduced after the original components are improved, particularly at 50-200 ℃, the temperature characteristic is obviously improved, and the X9T characteristic is satisfied. Fig. 6 to 8 are comparison of the characteristics of the modified composition and the original composition under a bias electric field. The bias characteristics of the improved composition are not as good as the original composition under low temperature and low electric field conditions, but the performance of the improved composition is superior to the original composition as the field strength increases. With the temperature rising to 200 ℃, the loss of the original components is greatly increased, but the improved components still maintain 93% of charge-discharge efficiency, so that the high dielectric constant and low loss characteristics under a high-temperature strong electric field are realized.
The above embodiments are only preferred embodiments of the present invention and are not intended to limit the scope of the present invention, but all changes made by adopting the design principle of the present invention and performing non-creative work on the basis thereof shall fall within the scope of the present invention.

Claims (9)

1. The energy storage ceramic is characterized by comprising the following components in percentage by weight:
(1-y-z)[(1-x)BaTiO 3 -xBiMeO 3 ]+yM+zQ(1)
wherein Me represents a single trivalent metal cation or a combination of multiple metal cations that are on average trivalent; m represents a linear dielectric; q represents an antiferroelectric body; x represents BiMeO 3 The molar fraction of (2) is [0.01,0.40 ]]The method comprises the steps of carrying out a first treatment on the surface of the y represents the mole fraction of the linear dielectric M, which is 0 or [0.05,0.4]The method comprises the steps of carrying out a first treatment on the surface of the z represents the molar fraction of the antiferroelectric Q, which is 0 or [0.05,0.4]The method comprises the steps of carrying out a first treatment on the surface of the The mole fractions of the linear dielectric M and the antiferroelectric Q are not simultaneously taken to be 0.
2. The high-temperature high-field high-dielectric low-loss energy storage ceramic according to claim 1, wherein said linear dielectric M is SrTiO 3 、SrZrO 3 、CaTiO 3 、CaZrO 3 One of them.
3. The high-temperature high-field high-dielectric low-loss energy storage ceramic according to claim 1, wherein said antiferroelectric body Q is NaNbO 3 、AgNbO 3 One of them.
4. The high-temperature high-field high-dielectric low-loss energy storage ceramic according to claim 1, wherein when the mole fraction of antiferroelectric body Q is 0, the composition expression of the energy storage ceramic is as follows:
(1-y)[(1-x)BaTiO 3 -xBiZn 23 (Nb 0.6 Ta 0.4 ) 13 O 3 ]+yCaZrO 3
wherein y is more than or equal to 0.05 and less than or equal to 0.4, and x is more than or equal to 0.01 and less than or equal to 0.4.
5. The high-temperature high-field high-dielectric low-loss energy-storage ceramic according to claim 1, wherein when the mole fraction of the linear dielectric M is 0, the composition expression of the energy-storage ceramic is as follows:
(1-z)[(1-x)BaTiO 3 -xBiScO 3 ]+zNaNbO 3
wherein, z is more than or equal to 0.05 and less than or equal to 0.4, and x is more than or equal to 0.01 and less than or equal to 0.4.
6. A method for preparing the high-temperature high-field high-dielectric low-loss energy storage ceramic according to any one of claims 1 to 5, which is characterized by comprising the following steps:
in BaCO 3 、TiO 2 、Bi 2 O 3 、ZnO、Nb 2 O 5 、Ta 2 O 5 、CaCO 3 And ZrO(s) 2 The preparation method comprises the following steps of (1) preparing raw materials according to the stoichiometric ratio of a chemical formula: ball milling, primary drying, presintering, secondary ball milling, secondary drying, granulating, tabletting, glue discharging and sintering, silver coating/metal spraying and testing;
in the steps of primary ball milling and secondary ball milling, zrO with the diameter of 1-10 mm is selected 2 Grinding the ball; adding a solvent medium in the steps of primary ball milling and secondary ball milling; the raw material, the medium of the solvent and ZrO 2 The mass ratio of the abrasive of the ball is 1:10 to 15:10 to 15 percent; the time of the primary ball milling is 16-24 hours; the time of the secondary ball milling is 6-12 hours; the ZrO 2 Ball milling is carried out in one direction, and the rotating speed is 250-350 r/min;
the temperature of the primary drying and the secondary drying is 60-70 ℃ and the drying time is 6-8 h;
in the presintering process, the temperature rising rate is 3 ℃/min, the presintering temperature is 850-1050 ℃, the heat preservation time is 2-4 h, and natural cooling is adopted;
the granulating is added with a binder; the adhesive takes absolute ethyl alcohol as a solvent and is dissolved with polyvinyl butyral with the mass percent of 3-10%; the mass ratio of the binder to the ceramic powder after secondary drying is 10% -20%;
in the glue discharging sintering, the heating rate is kept at 3 ℃/min, the glue discharging temperature is 500-700 ℃, and the heat preservation time is 2-4 h; sintering at 1150-1250 deg.c for 2-4 hr and naturally cooling;
in the silver coating/metal spraying process, the silver coating process is as follows: uniformly coating silver paste on the surface of the sintered ceramic sample or uniformly coating by adopting a screen printer, and treating for 10min at 500-700 ℃ to form a silver electrode; the metal spraying process is as follows: and sputtering and spraying gold on the two sides of the ceramic sample for 300-400 s by adopting a mask plate with a round hole diameter of 2-6 mm, and forming a gold electrode.
7. The method for preparing high-temperature high-field high-dielectric low-loss energy storage ceramic according to claim 6, wherein the solvent is ultrapure water or absolute ethanol or toluene.
8. The method for preparing high-temperature high-field high-dielectric low-loss energy-storage ceramic according to claim 7, wherein in the tabletting, the diameter of a die is 5-10 mm, the pressure applied on the die is 2MPa, and the thickness of a ceramic blank after tabletting is 0.2-1 mm.
9. The method for manufacturing high-temperature high-field high-dielectric low-loss energy storage ceramic according to claim 6, wherein the weighing error of the raw materials is not more than 0.1% of the total mass.
CN202310506422.5A 2023-05-08 2023-05-08 High-temperature strong-field high-dielectric low-loss energy storage ceramic and preparation method thereof Pending CN116444267A (en)

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