阅读说明：本技术 一种反铁电材料及其制备方法和含有其的电容器 (Antiferroelectric material, preparation method thereof and capacitor containing antiferroelectric material ) 是由 郝喜红 孟祥俊 赵烨 孙宁宁 李雍 于 2020-07-02 设计创作，主要内容包括：本发明公开了一种反铁电材料及其制备方法和含有其的电容器,该反铁电材料包括用通式(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>表示的反铁电体,其中,x的范围为0.3≤x≤0.5,y的范围为0≤y≤0.1,该反铁电材料可以用于制作储能电容器。本发明通过流延法所制备得到的锆钛锡酸铅镧反铁电厚膜电容器不仅能够达到90％～95％的超高储能效率,还具有较强的耐击穿性能,储能密度高,这为研发具有优异储能性能的介质储能电容器奠定了坚实的基础,具有很好的应用价值。(The invention discloses an antiferroelectric material, a preparation method thereof and a capacitor containing the antiferroelectric material, wherein the antiferroelectric material comprises a general formula (Pb) 0.94 La 0.04 )(Zr 1‑x‑y Sn x Ti y )O 3 The antiferroelectric material is represented, wherein x is in a range of 0.3-0.5, and y is in a range of 0-0.1, and can be used for manufacturing energy storage capacitors. The antiferroelectric thick film capacitor with lead lanthanum zirconate stannate prepared by the tape casting method not only can achieve 90-95% of ultrahigh energy storage efficiency, but also has stronger breakdown resistance and high energy storage density, thereby laying a solid foundation for developing a dielectric energy storage capacitor with excellent energy storage performance and having good application value.)

1. An antiferroelectric material characterized by comprising a compound represented by the general formula (Pb)_0.94La_0.04)(Zr_1-x-ySn_xTi_y)O₃The antiferroelectric is represented by the formula, wherein x is in the range of 0.3-0.5, and y is in the range of 0-0.1.

2. A method for preparing a ferroelectric material, comprising using a compound represented by the general formula (Pb)_0.94La_0.04)(Zr_1-x-ySn_xTi_y)O₃The preparation method of the antiferroelectric material of the ferroelectric is shown, wherein x is within the range of 0.3-0.5, and y is within the range of 0-0.1, and the preparation method of the ferroelectric film comprises the following steps:

s1: weighing Pb in a stoichiometric ratio in the general chemical composition₃O₄、La₂O₃、ZrO₂、SnO₂、TiO₂Raw material powder, preparing casting powder;

s2: and (4) ball-milling the casting powder obtained in the step (S1) with a solvent, a dispersing agent, an adhesive, a plasticizer and a homogenizing agent to obtain casting slurry, and then casting to form a thick film.

3. The method according to claim 2, wherein step S1 specifically includes:

s101: calculating and weighing Pb of corresponding mass according to stoichiometric ratio in chemical formula₃O₄、La₂O₃、ZrO₂、SnO₂、TiO₂Putting the raw material powder into a ball milling tank, and adding a ball milling medium to perform ball milling treatment for 12-24 hours;

s102: taking out the product obtained in the step S101, and then drying and presintering the product;

s103: performing ball milling treatment on the product obtained in the step S102 again, wherein the process is the same as that in the step S101;

s104: pouring the feed liquid obtained in the step S103 into a sand mill and carrying out sand milling treatment for 10-60 min;

s105: and (5) drying and grinding the product obtained in the step (S104) to obtain casting powder.

4. The method of claim 3, wherein in steps S101 and S103, the liquid ball milling medium comprises absolute ethanol and water; the solid ball milling medium comprises zirconia balls, agate balls and high-alumina balls with the diameter of 1-10 mm, and the ball milling rotating speed is 500-1000 rpm; the mass ratio of the powder to the solid ball-milling medium to the liquid ball-milling medium is 1: 1-3: 1-3; in the step S102 and the step S105, the drying temperature is 80-120 ℃, and the drying time is 5-10 h; in the step S102, the presintering temperature is 850-1000 ℃, the presintering time is 2-5 h, and the presintering temperature rise and fall gradient is 3-6 ℃/min; in step S104, the sanding medium comprises zirconia balls and high alumina balls with the diameter of 0.5 mm-3 mm, the sanding rotating speed is 1000 rpm-2500 rpm, and the mass ratio of the feed liquid to the ball milling medium is 1: 1 to 3.

5. The method according to claim 2, wherein step S2 specifically includes:

s201: carrying out dispersion ball milling on the casting powder obtained in the step S1 with a solvent and a dispersant for 8-16 h to obtain primary casting slurry;

s202: adding an adhesive, a plasticizer and a homogenizing agent into the primary casting slurry obtained in the step S201, and continuously performing ball milling for 4-10 hours to obtain uniform and stable casting slurry;

s203: carrying out vacuum defoaming treatment on the casting slurry obtained in the step S202 for 10-60 min;

s204: casting and airing the casting slurry after defoaming in the step S203, wherein the casting speed is 20-40 cm/min, the height of a scraper is 100-250 mu m, and the thickness of the obtained casting thick film is 10-60 mu m;

s205: and cutting the casting thick film dried in the step S204 into a rectangular thick film with a certain size.

6. The preparation method according to claim 5, characterized in that in the casting slurry, the casting powder accounts for 50-70% by mass, the solvent accounts for 15-45% by mass, the dispersant accounts for 0-3% by mass, the binder accounts for 3-8% by mass, the plasticizer accounts for 0-6% by mass, and the homogenizing agent accounts for 0-3% by mass; the rotating speed of the dispersion ball mill is 100 rpm-300 rpm; the ball milling medium is zirconia ball and high alumina ball with diameter of 3-10 mm.

7. The method according to claim 5 or 6, wherein the solvent comprises one or more of toluene, xylene, ethanol, methyl ethyl ketone, 1,1, 1-trichloroethylene, 1,1, 2-methylpyrrolidone; the dispersant comprises one or more of tributyl phosphate, ethoxylate and herring oil; the adhesive comprises one or more of polyvinyl butyral, polyvinyl alcohol, polymethyl methacrylate, polyethyl methacrylate, methyl cellulose and ethyl cellulose; the plasticizer comprises one or more of phthalate, polyethylene glycol, polypropylene and dibenzoate; the homogenizing agent is cyclohexanone.

8. An antiferroelectric thick film capacitor having an ultra-high energy storage efficiency, characterized by having a structure comprising the formula (Pb)_0.94La_0.04)(Zr_1-x-ySn_xTi_y)O₃The antiferroelectric material of the antiferroelectric is represented, wherein x is in the range of 0.3 to 0.5, and y is in the range of 0 to 0.1.

9. The method of making an antiferroelectric thick film capacitor having ultra-high energy storage efficiency of claim 8, comprising the steps of:

(1) printing a platinum electrode on the cut rectangular thick film by a screen printer;

(2) forming a multi-layer thick film capacitor by laminating and hot-pressing the rectangular thick film with the platinum electrode by using a laminating machine;

(3) carrying out cold isostatic pressing treatment on the multilayer thick film capacitor in the step (2) by using a cold isostatic press;

(4) cutting the product obtained in the step (3) by using a cutting machine to obtain a plurality of single multilayer thick film capacitors;

(5) performing plastic removal treatment on the single multilayer thick film capacitor green body obtained in the step (4) by using a box type furnace;

(6) and sintering the multilayer thick film capacitor subjected to plastic removal by using a box-type furnace to obtain the antiferroelectric thick film capacitor.

10. The preparation method according to claim 9, wherein the specific parameters of the lamination hot pressing in the step (2) are as follows: the temperature is 50-100 ℃, the pressure is 50-100 MPa, and the pressure maintaining time is 5-30 min; the cold isostatic pressing in the step (3) has the following body protection parameters: the pressure is 80MPa to 220MPa, and the pressure maintaining time is 10min to 40 min; the concrete parameters of plastic removal in the step (5) are as follows: the heating rate is 0.5 ℃/min to 5 ℃/min, the plastic discharging temperature is 400 ℃ to 700 ℃, and the furnace cooling is carried out after the heat preservation time is 2h to 6 h; the specific parameters of the sintering in the step (6) are as follows: the temperature rising and falling speed is 2 ℃/min to 6 ℃/min, the sintering temperature is 1100 ℃ to 1300 ℃, and the heat preservation time is 1h to 5 h.

Technical Field

The invention relates to the technical field of electronic materials, in particular to an antiferroelectric material, a preparation method thereof and a capacitor containing the antiferroelectric material, and especially relates to an antiferroelectric thick film capacitor with ultrahigh energy storage efficiency.

Background

In recent years, the development of electronic information products is changing day by day, and the development is rapidly progressing towards miniaturization, light weight, integration and wearable; however, the energy crisis associated with this is also increasing. In the face of such a severe challenge, the development and utilization of new materials and new energy sources, and the improvement and development of new processes and new technologies have become the focus of research in academia and industry.

Nowadays, a dielectric energy storage capacitor is receiving attention as a research hotspot in energy storage technology. The dielectric energy storage capacitor can be widely applied to the fields of business, civil use, military and the like, and is a core component of various pulse power systems and power electronic systems, including the fields of new energy automobiles, 5G communication, AI artificial intelligence, biological medical treatment, power distribution devices, pulse power weapons and the like. For a dielectric energy storage capacitor, energy storage density and energy storage efficiency are the most direct and important performance parameters for measuring and evaluating whether the performance of the dielectric energy storage capacitor is excellent or not. Many studies nowadays show that higher energy storage density is generally realized in dielectric energy storage materials, and particularly, higher energy storage density is often obtained in lead zirconate-based antiferroelectric dielectric energy storage materials, but the corresponding energy storage efficiency is not satisfactory, and the energy storage efficiency is far from being reported to exceed 90%. In the dielectric energy storage capacitor, the part of energy which is not available, namely the lost part of energy storage efficiency is often dissipated in the form of heat energy, and the part of loss can cause thermal breakdown and damage of the dielectric energy storage capacitor and greatly reduce the service life of the dielectric energy storage capacitor, so that hidden troubles are buried for safe use and long-term use of the dielectric energy storage capacitor. In view of the fact that the energy storage density and the energy storage efficiency in the medium energy storage material are often severely restricted, it is difficult to obtain a good value at the same time. Therefore, a new material and a new energy source, or a new process and a new technology are needed to solve the above problems.

Disclosure of Invention

The present invention has been made to overcome the above-mentioned drawbacks and disadvantages of the prior art, and an object of the present invention is to provide an antiferroelectric material, a method of preparing the same, and a capacitor comprising the same,

the purpose of the invention can be realized by the following technical scheme:

an antiferroelectric material comprises a compound represented by the general formula (Pb)_0.94La_0.04)(Zr_1-x-ySn_xTi_y)O₃The antiferroelectric is represented by the formula, wherein x is in the range of 0.3-0.5, and y is in the range of 0-0.1.

The antiferroelectric material takes lead zirconate ceramics as a system and enters a matrix through part of doping elements.

A process for preparing a ferroelectric material comprises using a compound of formula (Pb)_0.94La_0.04)(Zr_1-x-ySn_xTi_y)O₃The preparation method of the antiferroelectric material of the ferroelectric is shown, wherein x is within the range of 0.3-0.5, and y is within the range of 0-0.1, and the preparation method of the ferroelectric film comprises the following steps:

s1: weighing Pb in a stoichiometric ratio in the general chemical composition₃O₄、La₂O₃、ZrO₂、SnO₂、TiO₂Raw material powder, preparing casting powder;

s2: and (4) ball-milling the casting powder obtained in the step (S1) with a solvent, a dispersing agent, an adhesive, a plasticizer and a homogenizing agent to obtain casting slurry, and then casting to form a thick film.

Further, step S1 specifically includes:

s101: calculating and weighing Pb of corresponding mass according to stoichiometric ratio in chemical formula₃O₄、La₂O₃、ZrO₂、SnO₂、TiO₂Putting the raw material powder into a ball milling tank, and adding a ball milling medium to perform ball milling treatment for 12-24 hours;

s102: taking out the product obtained in the step S101, and then drying and presintering the product;

s103: performing ball milling treatment on the product obtained in the step S102 again, wherein the process is the same as that in the step S101;

s104: pouring the feed liquid obtained in the step S103 into a sand mill and carrying out sand milling treatment for 10-60 min;

s105: and (5) drying and grinding the product obtained in the step (S104) to obtain casting powder.

Further, in step S101 and step S103, the liquid ball milling medium includes absolute ethanol and water; the solid ball milling medium comprises zirconia balls, agate balls and high-alumina balls with the diameter of 1-10 mm, and the ball milling rotating speed is 500-1000 rpm; the mass ratio of the powder to the solid ball-milling medium to the liquid ball-milling medium is 1: 1-3: 1-3; in the step S102 and the step S105, the drying temperature is 80-120 ℃, and the drying time is 5-10 h; in the step S102, the presintering temperature is 850-1000 ℃, the presintering time is 2-5 h, and the presintering temperature rise and fall gradient is 3-6 ℃/min; in step S104, the sanding medium comprises zirconia balls and high alumina balls with the diameter of 0.5 mm-3 mm, the sanding rotating speed is 1000 rpm-2500 rpm, and the mass ratio of the feed liquid to the ball milling medium is 1: 1 to 3.

Further, step S2 specifically includes:

s201: carrying out dispersion ball milling on the casting powder obtained in the step S1 with a solvent and a dispersant for 8-16 h to obtain primary casting slurry;

s202: adding an adhesive, a plasticizer and a homogenizing agent into the primary casting slurry obtained in the step S201, and continuously performing ball milling for 4-10 hours to obtain uniform and stable casting slurry;

s203: carrying out vacuum defoaming treatment on the casting slurry obtained in the step S202 for 10-60 min;

s204: casting and airing the casting slurry after defoaming in the step S203, wherein the casting speed is 20-40 cm/min, the height of a scraper is 100-250 mu m, and the thickness of the obtained casting thick film is 10-60 mu m;

s205: and cutting the casting thick film dried in the step S204 into a rectangular thick film with a certain size.

Further, in the casting slurry, the mass percentage of the casting powder is 50-70%, the mass percentage of the solvent is 15-45%, the mass percentage of the dispersant is 0-3%, the mass percentage of the adhesive is 3-8%, the mass percentage of the plasticizer is 0-6%, and the mass percentage of the homogenizing agent is 0-3%; the rotating speed of the dispersion ball mill is 100 rpm-300 rpm; the ball milling medium is zirconia ball and high alumina ball with diameter of 3-10 mm.

Further, the solvent comprises one or more of toluene, xylene, ethanol, methyl ethyl ketone, 1,1, 1-trichloroethylene and 1,1, 2-methyl pyrrolidone; the dispersant comprises one or more of tributyl phosphate, ethoxylate and herring oil; the adhesive comprises one or more of polyvinyl butyral, polyvinyl alcohol, polymethyl methacrylate, polyethyl methacrylate, methyl cellulose and ethyl cellulose; the plasticizer comprises one or more of phthalate, polyethylene glycol, polypropylene and dibenzoate; the homogenizing agent is cyclohexanone.

An antiferroelectric thick film capacitor with ultra-high energy storage efficiency is disclosed, which comprises a material represented by the general formula (Pb)_0.94La_0.04)(Zr_1-x-ySn_xTi_y)O₃The antiferroelectric material of the antiferroelectric is represented, wherein x is in the range of 0.3 to 0.5, and y is in the range of 0 to 0.1.

The invention also provides a preparation method of the anti-ferroelectric thick film capacitor with ultrahigh energy storage efficiency, which comprises the following steps:

(1) printing a platinum electrode on the cut rectangular thick film by a screen printer;

(2) forming a multi-layer thick film capacitor by laminating and hot-pressing the rectangular thick film with the platinum electrode by using a laminating machine;

(3) carrying out cold isostatic pressing treatment on the multilayer thick film capacitor in the step (2) by using a cold isostatic press;

(4) cutting the product obtained in the step (3) by using a cutting machine to obtain a plurality of single multilayer thick film capacitors;

(5) performing plastic removal treatment on the single multilayer thick film capacitor green body obtained in the step (4) by using a box type furnace;

(6) and sintering the multilayer thick film capacitor subjected to plastic removal by using a box-type furnace to obtain the antiferroelectric thick film capacitor.

Further, the specific parameters of the lamination hot pressing in the step (2) are as follows: the temperature is 50-100 ℃, the pressure is 50-100 MPa, and the pressure maintaining time is 5-30 min. In addition, in order to prevent the capacitor from warping in the later glue discharging and sintering processes, blank film tapes with certain thickness are laminated and hot-pressed on the upper surface and the lower surface of the capacitor to form a sandwich structure.

Further, the body protection parameters of the cold isostatic pressing in the step (3) are as follows: the pressure is 80MPa to 220MPa, and the pressure maintaining time is 10min to 40 min.

Further, the concrete parameters of plastic removal in the step (5) are as follows: the heating rate is 0.5 ℃/min to 5 ℃/min, the plastic discharging temperature is 400 ℃ to 700 ℃, and the furnace cooling is carried out after the heat preservation time is 2h to 6 h.

Further, the specific parameters of the sintering in the step (6) are as follows: the temperature rising and falling speed is 2 ℃/min to 6 ℃/min, the sintering temperature is 1100 ℃ to 1300 ℃, and the heat preservation time is 1h to 5 h.

The invention has the beneficial effects that:

the antiferroelectric thick film capacitor with lead lanthanum zirconate stannate prepared by the tape casting method not only can achieve the ultrahigh energy storage efficiency of 90-95%, but also has higher breakdown electric field (E)_b) And higher energy storage density (W)_rec) Breakdown electric field (E) thereof_b) The range is 600kV/cm<E_b<850kV/cm, energy storage density (W)_rec) In the range of 10J/cm³<W_rec<16J/cm³The capacitor has strong breakdown resistance and high energy storage density, which lays a solid foundation for developing a medium energy storage capacitor with excellent energy storage performance and has good application value.

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 ferroelectric hysteresis loop of a PLZST-1 antiferroelectric thick film capacitor prepared in example 1 of this invention;

FIG. 2 is a ferroelectric hysteresis loop of a PLZST-2 antiferroelectric thick film capacitor prepared in example 2 of this invention;

FIG. 3 is a ferroelectric hysteresis loop of a PLZST-3 antiferroelectric thick film capacitor prepared in example 3 of this invention;

FIG. 4 is a plot of the hysteresis loop of a PLZST-4 antiferroelectric thick film capacitor made according to comparative example 1 of the present invention;

FIG. 5 is a plot of the hysteresis loop of a PLZST-5 antiferroelectric cast ceramic prepared in comparative example 2 of the present invention;

FIG. 6 is a graph showing energy storage density and energy storage efficiency of examples 1 to 3 and comparative examples 1 to 2 according to the present invention;

FIG. 7 is a graph showing the breakdown field strength of examples 1 to 3 of the present invention and comparative examples 1 to 2.

Wherein PLZST-1 in fig. 1 refers to a specific composition PLZST antiferroelectric thick film capacitor prepared in example 1; PLZST-2 in fig. 2 refers to a specific composition PLZST antiferroelectric thick film capacitor prepared in example 2; PLZST-3 in fig. 3 refers to a specific composition PLZST antiferroelectric thick film capacitor prepared in example 3; PLZST-4 in fig. 4 refers to a PLZST antiferroelectric thick film capacitor of a specific composition prepared in comparative example 1; PLZST-5 in fig. 5 refers to a PLZST antiferroelectric ceramic of a specific composition prepared in comparative example 2.

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.