High-energy-storage-density low-lead-zirconate-titanate-based antiferroelectric ceramic and preparation method thereof
阅读说明：本技术 高储能密度低钛锆酸铅基反铁电陶瓷及其制备方法 (High-energy-storage-density low-lead-zirconate-titanate-based antiferroelectric ceramic and preparation method thereof ) 是由 郝喜红 孟祥俊 李雍 赵烨 于 2020-05-14 设计创作，主要内容包括：本发明公开了一种高储能密度低钛锆酸铅基反铁电陶瓷及其制备方法,该低钛锆酸铅基反铁电陶瓷材料的化学组成通式为：(Pb<Sub>0.94</Sub>La<Sub>0.04</Sub>)(Zr<Sub>1-x-y</Sub>Sn<Sub>x</Sub>Ti<Sub>y</Sub>)O<Sub>3</Sub>,其中,0≤x≤0.5,0≤y≤0.03。本发明通过调控不同的Zr/Sn/Ti比例,并借助流延成型的工艺制备得到的低钛锆酸铅基反铁电陶瓷材料可以在1100-1300℃温度范围内烧结,且本发明制备得到的低钛锆酸铅基反铁电陶瓷材料在室温条件下兼备高相变电场、高击穿电场、高极化强度的特点,并能够具有非常高的储能密度和储能效率,弥补了传统法制备锆酸铅基反铁电陶瓷材料相变电场低、击穿电场低、储能密度低的技术缺陷,拓宽了其在高功率储能材料领域的研发和应用。(The invention discloses a high-energy-storage-density low-lead-zirconate-titanate-based antiferroelectric ceramic and a preparation method thereof, wherein the chemical composition general formula of the low-lead-zirconate-titanate-based antiferroelectric ceramic material is as follows: (Pb) 0.94 La 0.04 )(Zr 1‑x‑y Sn x Ti y )O 3 Wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.03. The low-titanium lead zirconate-based antiferroelectric ceramic material prepared by regulating different Zr/Sn/Ti ratios and by means of tape casting can be sintered within the temperature range of 1100-1300 ℃, and the low-titanium lead zirconate-based antiferroelectric ceramic material prepared by the methodThe electro-ceramic material has the characteristics of high phase-change electric field, high breakdown electric field and high polarization strength at room temperature, has very high energy storage density and energy storage efficiency, overcomes the technical defects of low phase-change electric field, low breakdown electric field and low energy storage density of the lead zirconate-based antiferroelectric ceramic material prepared by the traditional method, and widens the research, development and application of the lead zirconate-based antiferroelectric ceramic material in the field of high-power energy storage materials.)
1. The high-energy-storage-density low-lead-zirconate-titanate-based antiferroelectric ceramic material is characterized by comprising the following chemical components in a general formula: (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3Wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.03.
2. The method for preparing the high energy storage density low lead zirconate titanate-based antiferroelectric ceramic material according to claim 1, which comprises the following steps:
1) preparing casting powder: according to the chemical formula (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3Stoichiometric ratio of Pb in3O4Raw material powder, La2O3Raw material powder, ZrO2Raw material powder and SnO2Raw material powder and TiO2Ball-milling the raw material powder in a ball-milling tank to obtain (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3Casting powder;
2) preparing casting slurry: the (Pb) obtained in the step 1)0.94La0.04)(Zr1-x-ySnxTiy)O3Mixing the casting powder with a solvent, a dispersant, an adhesive, a plasticizer and a homogenizing agent to obtain uniform and stable casting slurry;
3) casting and forming: the (Pb) obtained in the step 2)0.94La0.04)(Zr1-x-ySnxTiy)O3The casting slurry is subjected to casting treatment to obtain (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3Casting a thick film blank sheet, and cutting, laminating and pressing the thick film blank sheet to obtain a single ceramic green body;
4) plastic removal and sintering: the (Pb) obtained in the step 3)0.94La0.04)(Zr1-x-ySnxTiy)O3Performing plastic removal and sintering treatment on the ceramic green body to obtain (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3An antiferroelectric ceramic.
3. The method according to claim 2, wherein (Pb) in the step 1)0.94La0.04)(Zr1-x-ySnxTiy)O3The preparation method of the casting powder comprises the following steps:
firstly, ball milling: mixing the weighed total raw material powder with a ball milling medium, and performing ball milling to obtain primary ball milling powder;
② drying and presintering, drying and presintering the primary ball-milled powder to obtain (Pb)0.94La0.04)(Zr1-x- ySnxTiy)O3Pre-burning powder;
③ ball-milling twice (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3Performing secondary ball milling on the pre-sintered powder according to the ball milling process in the step ①, and then drying according to the drying process in the step ② to obtain (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3And (3) casting the powder.
4. The preparation method according to claim 3, wherein the mass ratio of the raw material powder, the absolute ethyl alcohol and the zirconia balls in the step 1) is 1: 1-2: 1-2; the diameter of the zirconia ball is 1-10 mm; the ball milling speed is 300-600rpm, and the ball milling time is 20-24 h; the drying temperature of the primary ball-milling powder is 80-100 ℃, and the drying time is 3-6 h; the pre-sintering temperature is 850 ℃ and 950 ℃, the pre-sintering time is 1-4h, and the pre-sintering temperature rise and fall gradient is 3-6 ℃/min.
5. The method according to claim 2, wherein the solvent is a mixture of toluene and absolute ethanol; the dispersant is tributyl phosphate; the adhesive is polyvinyl butyral; the plasticizer is one or more of polyethylene glycol-400 and phthalate; the homogenizing agent is cyclohexanone.
6. A producing method according to claim 2, characterized in that said casting paste comprises the following components in weight percent based on the weight of said casting paste: (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3Casting powder 50-70%, toluene 10-30%, anhydrous ethanol 5-15%, tributyl phosphate 0-3%, polyvinyl butyral 3-8%, polyethylene glycol-4000-3%, phthalate 0-3%And 0-3% of cyclohexanone.
7. The method according to claim 2, wherein the (Pb) in the step 2)0.94La0.04)(Zr1-x- ySnxTiy)O3The casting slurry is prepared according to the following casting steps:
s1: weighing raw materials, a solvent and a dispersing agent into a ball milling tank, and ball milling for 8-12h at the rotating speed of 50-200rpm to uniformly mix the raw materials, the solvent and the dispersing agent;
s2: adding the polyvinyl butyral dissolved by the solvent and the rest components in the formula into a ball milling tank, and continuing to perform ball milling under the ball milling condition in the step S1 to obtain (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3And casting the slurry.
8. The production method as claimed in claim 2, wherein the step 3) employs a casting rate of 20 to 40cm/min and a blade height of 100 and 250 μm to obtain (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3The thickness of the casting thick film blank sheet is 10-60 mu m; the adopted hot-press forming process comprises the following steps: the temperature is 30-100 ℃, the pressure is 2-10MPa, and the pressure maintaining time is 5-30 min; the adopted cold isostatic pressing process comprises the following steps: the pressure is 100-.
9. The preparation method as claimed in claim 2, wherein the plastic removal process adopted in step 4) comprises raising the temperature to 450-650 ℃ at a temperature raising rate of 0.5-3 ℃/min and maintaining the temperature for 2-6h, and then cooling with the furnace.
10. The preparation method according to claim 2, wherein the sintering process adopted in step 4) is heating to 1100-1300 ℃ at a heating and cooling rate of 2-6 ℃/min and keeping the temperature for 2-5 h.
Technical Field
The invention relates to the technical field of electronic functional materials, in particular to a high-energy-storage-density low-lead-zirconate-titanate-based antiferroelectric ceramic and a preparation method thereof.
Background
The progress of the times and the development of science and technology bring great convenience to daily living of people, meanwhile, the people are also aggravated to develop and predate energy materials, and the energy crisis becomes a global problem covering the world due to the continuous consumption of energy. The coming of the 5G era sets higher requirements for electronic components, and electronic products are more and more diverse, and are rapidly developing towards the direction of miniaturization, integration and wearability. Based on the above situation, inheriting the concept of green sustainable development, continuously improving the utilization rate of the traditional energy and vigorously developing a green and clean novel energy storage material to replace the traditional energy material are increasingly important.
As one of electric energy storage methods, ceramic-based dielectric energy storage capacitors are widely used in the fields of business, civil use, military and the like, and are core components of various pulse power systems including new energy vehicles, 5G communication, power distribution devices, pulse power weapons and the like. The research on energy storage dielectric ceramic materials mainly focuses on three major categories of linear dielectric ceramic materials, ferroelectric ceramic materials and antiferroelectric ceramic materials. Among them, linear dielectric ceramics tend to have a low energy storage density due to their low dielectric constant; ferroelectric ceramics have a lower energy storage density and efficiency due to their high remanent polarization. In contrast to linear dielectric ceramics and ferroelectric ceramic materials, antiferroelectric ceramic materials have nearly zero remnant polarization and undergo an antiferroelectric-ferroelectric phase transition (E)AFE-FE) The macroscopic polarization strength is obviously enhanced in the process, so that high energy storage density is expected to be obtained.
The lead zirconate-based antiferroelectric ceramic material has a double-ferroelectric hysteresis loop, belongs to a typical perovskite structure, and can generate E under the induction of an external electric fieldAFE-FEDuring this phase transition, a significant increase in the polarization intensity occursAdditionally, a high energy storage density can be achieved. The lead zirconate-based antiferroelectric ceramic material prepared by the traditional method at present has poor compactness and breakdown strength (E)b) Lower, often up to EAFE-FEBreakdown has previously occurred, thus resulting in limited utility. In addition, the energy storage efficiency of the lead zirconate-based antiferroelectric ceramic material is low due to the hysteresis of the reversible phase transition process of the lead zirconate-based antiferroelectric ceramic material. Therefore, the energy storage density and the energy storage efficiency of the lead zirconate-based antiferroelectric ceramic dielectric material are often severely restricted, and the excellent value is difficult to obtain simultaneously. Therefore, a new and effective preparation process is needed to solve the above problems.
For lead zirconate-based antiferroelectric ceramic energy storage components and parts, WrecAnd η are two important parameters for evaluating the energy storage performance, and the total energy storage density (W)tot) Releasable energy storage density (W)rec) And efficiency (η) may be calculated by the following equation:
wherein E represents the electric field strength, P represents the polarization strength, PrAnd PmaxRepresenting residual polarization and saturation polarization. As can be seen from the above formula, the lead zirconate-based antiferroelectric ceramic material has high energy storage density, and E thereofbHigh, PrSmall, PmaxIs large so as to ensure a high energy storage density.
Compared with the traditional method, the lead zirconate-based antiferroelectric ceramic prepared by the tape casting method has higher EbEnsure that it reaches EAFE-FEThe breakdown phenomenon still does not occur during the preparation, thereby making up for the preparation of the lead zirconate-based antiferroelectric ceramic material E by the traditional methodbLow cost. Meanwhile, the lead zirconate-based antiferroelectric ceramic material prepared by the tape casting method has a high phase-change electric field, and also obtains high polarization strength under a breakdown electric field, so that the high energy storage density is guaranteed, and the development and application of the lead zirconate-based antiferroelectric ceramic material in the field of high-power energy storage components are facilitated to be widened.
Disclosure of Invention
The invention provides a lead zirconate titanate-based antiferroelectric ceramic material with high energy storage density and low titanium, which overcomes the technical defects of low phase change electric field, low breakdown field strength and low energy storage density of the traditional method by adopting a component regulation and casting method, and has the characteristics of high phase change electric field and high breakdown field strength, and finally realizes high energy storage density.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a low-lead-zirconate-titanate-based antiferroelectric ceramic material with high energy storage density, which has the chemical composition general formula: (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3(abbreviated as PLZST), wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.03.
The invention also aims to provide a preparation method of the high-energy-storage-density low-lead-zirconate-titanate-based antiferroelectric ceramic material, which comprises the following steps:
1) preparing casting powder: according to the chemical formula (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3Stoichiometric ratio of Pb in3O4Raw material powder, La2O3Raw material powder, ZrO2Raw material powder and SnO2Raw material powder and TiO2Ball-milling the raw material powder in a ball-milling tank to obtain (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3Casting powder;
2) preparing casting slurry: the (Pb) obtained in the step 1)0.94La0.04)(Zr1-x-ySnxTiy)O3Mixing the casting powder with a solvent, a dispersant, an adhesive, a plasticizer and a homogenizing agent to obtain uniform and stable casting slurry;
3) casting and forming: the (Pb) obtained in the step 2)0.94La0.04)(Zr1-x-ySnxTiy)O3The casting slurry is subjected to casting treatment to obtain (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3Casting a thick film blank sheet, and cutting, laminating and pressing the thick film blank sheet to obtain a single ceramic green body;
4) plastic removal and sintering: the (Pb) obtained in the step 3)0.94La0.04)(Zr1-x-ySnxTiy)O3Performing plastic removal and sintering treatment on the ceramic green body to obtain (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3An antiferroelectric ceramic.
Preferably, step 1) (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3The preparation method of the casting powder comprises the following steps:
firstly, ball milling: mixing the weighed total raw material powder with a ball milling medium, and performing ball milling to obtain primary ball milling powder;
② drying and presintering, drying and presintering the primary ball-milled powder to obtain (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3Pre-burning powder;
③ ball-milling twice (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3Performing secondary ball milling on the pre-sintered powder according to the ball milling process in the step ①, and then drying according to the drying process in the step ② to obtain (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3And (3) casting the powder.
Further preferably, the mass ratio of the raw material powder, the absolute ethyl alcohol and the zirconia balls in the step 1) is 1: 1-2: 1-2; the diameter of the zirconia ball is 1-10 mm; the ball milling speed is 300-600rpm, and the ball milling time is 20-24 h; the drying temperature of the primary ball-milling powder is 80-100 ℃, and the drying time is 3-6 h; the pre-sintering temperature is 850 ℃ and 950 ℃, the pre-sintering time is 1-4h, and the pre-sintering temperature rise and fall gradient is 3-6 ℃/min.
Preferably, the solvent is a mixture of toluene and absolute ethyl alcohol; the dispersant is tributyl phosphate; the adhesive is polyvinyl butyral; the plasticizer is one or more of polyethylene glycol-400 and phthalate; the homogenizing agent is cyclohexanone.
Preferably, the casting slurry comprises the following components in weight percent based on the weight of the casting slurry: (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3Casting powder 50-70%, toluene 10-30%, absolute ethyl alcohol 5-15%, tributyl phosphate 0-3%, polyvinyl butyral 3-8%, polyethylene glycol-4000-3%, phthalate 0-3%, and cyclohexanone 0-3%.
Preferably, (Pb) described in step 2)0.94La0.04)(Zr1-x-ySnxTiy)O3The casting slurry is prepared according to the following casting steps:
s1: weighing raw materials, a solvent and a dispersing agent into a ball milling tank, and ball milling for 8-12h at the rotating speed of 50-200rpm to uniformly mix the raw materials, the solvent and the dispersing agent;
s2: adding the polyvinyl butyral dissolved by the solvent and the rest components in the formula into a ball milling tank, and continuing to perform ball milling under the ball milling condition in the step S1 to obtain (Pb)0.94La0.04)(Zr1-x-ySnxTiy)O3And casting the slurry.
Preferably, the step 3) employs a casting rate of 20 to 40cm/min and a blade height of 100-0.94La0.04)(Zr1-x-ySnxTiy)O3The thickness of the casting thick film blank sheet is 10-60 mu m; the adopted hot-press forming process comprises the following steps: the temperature is 30-100 ℃, the pressure is 2-10MPa, and the pressure maintaining time is 5-30 min; the adopted cold isostatic pressing process comprises the following steps: the pressure is 100-.
Preferably, the plastic removal process adopted in the step 4) is heating to 450-650 ℃ at a heating rate of 0.5-3 ℃/min, preserving the heat for 2-6h, and then cooling along with the furnace.
Preferably, the sintering process adopted in the step 4) is heating to 1100-1300 ℃ at a heating and cooling rate of 2-6 ℃/min and keeping the temperature for 2-5 h.
The invention obtains the (Pb) which can be sintered in the temperature range of 1100-0.94La0.04)(Zr1-x-ySnxTiy)O3An antiferroelectric ceramic material.
(Pb) produced by the present invention0.94La0.04)(Zr1-x-ySnxTiy)O3The thickness of the antiferroelectric ceramic material is between 80 and 120 μm.
The invention has the beneficial effects that:
the low-titanium lead zirconate-based antiferroelectric ceramic material prepared by regulating different Zr/Sn/Ti ratios and by means of the tape casting process can be sintered at the temperature range of 1100-1300 ℃, and the low-titanium lead zirconate-based antiferroelectric ceramic material prepared by the method has high phase transition electric field (346kV/cm), high breakdown electric field (400kV/cm) and high polarization strength (52.8 mu C/cm) at room temperature2) Can have very high energy storage density (12.3J/cm)3) And the energy storage efficiency (80.3 percent), the technical defects of low phase-change electric field, low breakdown electric field and low energy storage density of the lead zirconate-based antiferroelectric ceramic material prepared by the traditional method are overcome, and the research, development and application of the lead zirconate-based antiferroelectric ceramic material in the field of high-power energy storage materials are widened.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is a graph showing the electric hysteresis of PLZST antiferroelectric ceramics prepared in examples 1-3 of the present invention and comparative example 1;
FIG. 2 is a graph of energy storage density at different electric fields for PLZST antiferroelectric ceramic prepared in example 1 of the present invention;
FIG. 3 is a graph of energy storage density at different electric fields for PLZST antiferroelectric ceramic prepared in example 2 of the present invention;
FIG. 4 is a graph of energy storage density at different electric fields for PLZST antiferroelectric ceramic prepared in example 3 of the present invention;
FIG. 5 is a graph of energy storage density at different electric fields for PLZST antiferroelectric ceramics prepared in comparative example 1 of the present invention;
fig. 6 is a graph showing the energy storage density and efficiency of PLZST antiferroelectric ceramics prepared in examples 1-3 of the present invention and comparative example 1.
Wherein PLZST-1 in fig. 1 refers to the PLZST antiferroelectric ceramic prepared in example 1, and the corresponding ferroelectric hysteresis loop is the one indicated by numeral 1 in the figure; PLZST-2 refers to the PLZST antiferroelectric ceramic prepared in example 2, and the corresponding ferroelectric hysteresis loop is the one indicated by numeral 2 in the figure; PLZST-3 refers to the PLZST antiferroelectric ceramic prepared in example 3, and the corresponding ferroelectric hysteresis loop is the one indicated by numeral 3 in the figure; PLZST-4 in fig. 1 indicates the PLZST antiferroelectric ceramic prepared in practical example 1, and the corresponding hysteresis loop is the one indicated by numeral 4 in the figure.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified. In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.