CN113429203A - Lead zirconate stannate thick film ceramic material with high breakdown electric field resistance and preparation method thereof - Google Patents
Lead zirconate stannate thick film ceramic material with high breakdown electric field resistance and preparation method thereof Download PDFInfo
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Abstract
The invention provides a lead zirconate stannate thick film ceramic material with high breakdown electric field resistance and a preparation method thereof, wherein the preparation method comprises the following steps: weighing the raw materials according to a preset stoichiometric ratio, placing the raw materials in a nylon ball milling tank, adding excessive 3 wt% of PbO, and carrying out ball milling to obtain a first product; drying and sieving the first product to obtain first ceramic powder; pre-burning the first ceramic powder in a muffle furnace, and respectively doping glass powder into the pre-burned first ceramic powder according to different mass fractions after pre-burning; performing secondary ball milling, drying and sieving to obtain second ceramic powder; placing the mixture in a tumbling mill tank, adding a dispersing agent and a solvent for tumbling to obtain premixed slurry, adding a binder for continuous tumbling, adding the solvent, the binder and the plasticizer for continuous tumbling to obtain casting slurry; and carrying out tape casting molding on the tape casting slurry through a tape casting machine, and obtaining the lead zirconate stannate thick film ceramic material with high breakdown electric field resistance after carrying out isostatic pressing and binder removal sintering. The invention forms the thick film ceramic with high breakdown electric field resistance and high energy storage density.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a lead zirconate stannate thick film ceramic material with high breakdown electric field resistance and a preparation method thereof.
Background
As the demand for smaller and lighter portable electronic devices increases, the development of advanced energy storage materials and related technologies has been a research focus in academia and manufacturing industries, where batteries and capacitors are the two most prominent energy storage devices today. Batteries are capable of converting electrical energy to chemical energy, typically with relatively high energy densities (-100 Wh/kg). However, since the carrier moving speed is too slow, the battery can output limited electric energy in a unit time. The capacitor, on the contrary, can discharge the stored charge in a very short time (<100 ns), thus generating very large energy in a short time. For many practical applications, such as electric vehicles, spacecraft, medical equipment, pulsed energy systems, weaponry, etc., not only relatively high energy densities are required, but also high power densities are essential. The energy storage capacitor has the functions of high power density, high charging and discharging speed and cyclic aging resistance, is suitable for extreme environments such as high temperature and high pressure, and has the advantage of stable performance, thereby playing an increasingly important role in electric and electronic systems.
Historically, many different dielectric materials, from paper, plastics to ceramics, have been used to fabricate electrostatic capacitors. Capacitors are nowadays made of polymers or ceramics because they have their own characteristics in terms of capacitance, dielectric loss, resistance to breakdown field strength, etc. The breakdown-resistant electric field strength of the antiferroelectric material is a key parameter for determining the maximum electric field that the antiferroelectric material can bear. For high dielectric constant materials, the storage density can be derived from the following equation:
it can be seen that the energy density is directly related to the dielectric breakdown strength (Emax) of the material, and a higher breakdown-resistant electric field strength necessarily results in a higher energy density. The development of high energy density antiferroelectric materials has long been limited by the relatively low breakdown field strength. More importantly, the antiferroelectric material is different from other dielectric materials in that the polarization strength of the antiferroelectric material has a nonlinear relationship with the electric field strength, and higher polarization strength P is often required in the ferroelectric phase. However, most orthotropic lead zirconate-based antiferroelectric materials break down before reaching the Antiferroelectric (AFE) -Ferroelectric (FE) phase transition because the AFE-FE phase transition electric field is higher than the maximum electric field that a particular antiferroelectric material can withstand. Although the AFE-FE critical transition electric field can be achieved in a thin film form, thus exhibiting a higher energy storage density, the intrinsic energy density thereof needs to be further improved. Therefore, if the breakdown field strength of the antiferroelectric material can be effectively improved, a problem to be solved is needed.
Disclosure of Invention
The invention provides a lead zirconate stannate thick film ceramic material with high breakdown electric field resistance and a preparation method thereof for solving the technical problems.
The invention provides a preparation method of a lead zirconate stannate thick film ceramic material with high breakdown electric field resistance, which comprises the following steps:
step S1: PbO, La2O3、ZrO2、SnO2Weighing and placing the mixture in a nylon ball milling tank according to a preset stoichiometric ratio, adding excessive 3 wt% of PbO, and carrying out ball milling to obtain a first product;
step S2: drying and sieving the first product to obtain first ceramic powder;
step S3: pre-sintering the first ceramic powder in a muffle furnace, and then pre-sintering the first ceramic powder B2O3-the ZnO glass powder is respectively doped into the pre-sintered first ceramic powder according to different mass fractions;
step S4: performing secondary ball milling, drying and sieving to obtain second ceramic powder;
step S5: placing the second ceramic powder in a tumbling tank, adding a dispersing agent and a solvent for tumbling to obtain premixed slurry, adding a binder for continuous tumbling, adding the solvent, the binder and the plasticizer for continuous tumbling to obtain casting slurry;
step S6: and carrying out tape casting molding on the tape casting slurry through a tape casting machine, and obtaining the lead zirconate stannate thick film ceramic material with high breakdown electric field resistance after carrying out isostatic pressing and binder removal sintering.
Further, the ball milling in the steps S1 and S4 is specifically as follows:
the ball milling medium is zirconium dioxide balls with the diameter of 3mm and 5mm, and the mass ratio is about 3: 2; adopting wet ball milling, and adding a proper amount of alcohol, wherein the raw materials comprise: alcohol: zirconium balls = 1: 2: 5; and (3) ball milling is carried out by adopting a common planetary ball mill, the rotating speed is set to be 250 r/min, and the ball milling time is 24 h.
Further, the drying and screening in the steps S2 and S4 are as follows:
putting the ball-milled ceramic powder into an oven for drying at the temperature of about 60 ℃ for more than 12 h; after drying, the ceramic powder is respectively sieved by a 40-mesh sieve and a 80-mesh sieve.
Further, in step S3, the pre-firing temperature is 900 ℃ and the time is 2 hours.
Further, the step S5 specifically includes the following steps:
placing the second ceramic powder obtained by the treatment of the step S4 in a tumbling tank, adding a dispersing agent and a solvent, and then tumbling at the rotating speed of 200 rpm for 20 hours to obtain premixed slurry; then adding a binder and tumbling for 10 hours at the rotating speed of 200 rpm; and then adding a solvent, a binder and a plasticizer, and carrying out ball milling for 12-16 h at the rotating speed of 200 rpm to obtain uniformly mixed casting slurry with the viscosity of 600-800 mPa & s.
Further, in step S6, the linear speed of the casting machine film belt is about 0.20, and the drying temperature is 40 ℃.
Further, in step S6, the pressure of the warm isostatic pressing was set to 30 MPa, the temperature was set to 60 ℃, and the pressure holding time was 5 min.
Further, in step S6, the binder removal sintering is specifically at 400 ℃ and the ceramic sintering temperature is 1200 ℃.
On the other hand, the invention also provides a lead zirconate stannate thick film ceramic material with high breakdown electric field resistance, which is prepared by the preparation method.
The invention has the beneficial effects that: the invention adopts a solid phase method to synthesize PLZS powder and is doped with sintering aid B with different doping amounts2O3ZnO glass, and preparing the thickness-controllable lead zirconate stannate thick film ceramic by a tape casting process. The pre-sintered powder obtained by X-ray diffraction (XRD) is of a perovskite structure, and the sintered crystal grains of the sample are uniformly and compactly distributed and have the size of about 1-2 mu m when observed by a scanning electron microscope. At room temperature, the electric hysteresis loop of the sample changes from an antiferroelectric phase to a ferroelectric phase along with the increase of the electric field, and the composition of the sample is proved to be in a PLZS antiferroelectric phase region.
And calculating the energy storage density and the energy storage efficiency of each sample according to the obtained electric hysteresis loop, so that the ceramic sample can bear higher electric field intensity under the condition of low glass doping amount of PLZS, and higher energy storage density and energy storage efficiency can be obtained. At 0.10 wt% BZ and 0.25 wt% BZ loadings, the samples were able to withstand 560 kV/cm and 685 kV/cm electric fields, respectively, without breakdown. By adding the glass sintering aid for sintering, the glass with a relatively low melting point can form a liquid phase firstly to wrap the crystal grains. According to the liquid phase sintering mechanism, the force exerted by the wet liquid phase and the nucleation rearrangement mechanism result in densification of the solid phase and reduce defects in the sample. The thick film ceramic has the advantages of small size and good compatibility with an integrated circuit, and meanwhile, if the glass sintering aid is added for sintering, the density of the thick film ceramic is increased, so that the thick film ceramic with high breakdown-resistant electric field and high energy storage density is finally formed, and the thick film ceramic has great significance for the practical application of the antiferroelectric/ferroelectric ceramic in the technical field of pulse power.
Drawings
FIG. 1 shows the incorporation of different mass fractions B2O3Pb of-ZnO0.97La0.02 (Zr0.50Sn0.50)0.98O3X-ray diffraction pattern of the powder.
FIG. 2 is a graph of incorporation of 0.25 wt% B2O3Pb of-ZnO0.97La0.02 (Zr0.50Sn0.50)0.98O3SEM image of thick film ceramic sintered at 1200 deg.C for 3 h.
FIG. 3 is PLZS +0 wt% B2O3-hysteresis diagram of ZnO measured under electric field.
FIG. 4 is PLZS +0.10 wt% B2O3-hysteresis diagram of ZnO measured under electric field.
FIG. 5 is PLZS +0.25 wt% B2O3-hysteresis diagram of ZnO measured under electric field.
FIG. 6 is PLZS +0.50 wt% B2O3-hysteresis diagram of ZnO measured under electric field.
FIG. 7 shows a modification B2O3Energy storage performance diagram of ZnO glass doping PLZS.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used only for convenience of description and simplicity of description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be considered as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, "above" or "below" a first feature means that the first and second features are in direct contact, or that the first and second features are not in direct contact but are in contact with each other via another feature therebetween. Also, the first feature being "on," "above" and "over" the second feature includes the first feature being directly on and obliquely above the second feature, or merely indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly under and obliquely below the second feature, or simply meaning that the first feature is at a lesser elevation than the second feature.
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings.
As shown in FIGS. 1 to 7, the invention provides a preparation method of a lead zirconate stannate thick film ceramic material with high breakdown electric field resistance, which comprises the following steps:
step S1: PbO, La2O3、ZrO2、SnO2Weighing and placing the mixture in a nylon ball milling tank according to a preset stoichiometric ratio, adding excessive 3 wt% of PbO, and carrying out ball milling to obtain a first product;
step S2: drying and sieving the first product to obtain first ceramic powder;
step S3: pre-sintering the first ceramic powder in a muffle furnace, and then pre-sintering the first ceramic powder B2O3-the ZnO glass powder is respectively doped into the pre-sintered first ceramic powder according to different mass fractions;
step S4: performing secondary ball milling, drying and sieving to obtain second ceramic powder;
step S5: placing the second ceramic powder in a tumbling tank, adding a dispersing agent and a solvent for tumbling to obtain premixed slurry, adding a binder for continuous tumbling, adding the solvent, the binder and the plasticizer for continuous tumbling to obtain casting slurry;
step S6: and carrying out tape casting molding on the tape casting slurry through a tape casting machine, and obtaining the lead zirconate stannate thick film ceramic material with high breakdown electric field resistance after carrying out isostatic pressing and binder removal sintering.
The invention adopts a solid phase method to synthesize PLZS powder and is doped with sintering aid B with different doping amounts2O3ZnO glass, and preparing the thickness-controllable lead zirconate stannate thick film ceramic by a tape casting process. The pre-sintered powder obtained by X-ray diffraction (XRD) is of a perovskite structure, and the sintered crystal grains of the sample are uniformly and compactly distributed and have the size of about 1-2 mu m when observed by a scanning electron microscope. At room temperature, the electric hysteresis loop of the sample changes from an antiferroelectric phase to a ferroelectric phase along with the increase of the electric field, and the composition of the sample is proved to be in a PLZS antiferroelectric phase region.
And calculating the energy storage density and the energy storage efficiency of each sample according to the obtained electric hysteresis loop, so that the ceramic sample can bear higher electric field intensity under the condition of low glass doping amount of PLZS, and higher energy storage density and energy storage efficiency can be obtained. At 0.10 wt% BZ and 0.25 wt% BZ loadings, the samples were able to withstand 560 kV/cm and 685 kV/cm electric fields, respectively, without breakdown. By adding the glass sintering aid for sintering, the glass with a relatively low melting point can form a liquid phase firstly to wrap the crystal grains. According to the liquid phase sintering mechanism, the force exerted by the wet liquid phase and the nucleation rearrangement mechanism result in densification of the solid phase and reduce defects in the sample. The thick film ceramic has the advantages of small size and good compatibility with an integrated circuit, and meanwhile, if the glass sintering aid is added for sintering, the density of the thick film ceramic is increased, so that the thick film ceramic with high breakdown-resistant electric field and high energy storage density is finally formed, and the thick film ceramic has great significance for the practical application of the antiferroelectric/ferroelectric ceramic in the technical field of pulse power.
In an alternative embodiment, the ball milling in step S1 and step S4 is as follows:
the ball milling medium is zirconium dioxide balls with the diameter of 3mm and 5mm, and the mass ratio is about 3: 2; adopting wet ball milling, and adding a proper amount of alcohol, wherein the raw materials comprise: alcohol: zirconium balls = 1: 2: 5; and (3) ball milling is carried out by adopting a common planetary ball mill, the rotating speed is set to be 250 r/min, and the ball milling time is 24 h. The drying and screening in the steps S2 and S4 are as follows: putting the ball-milled ceramic powder into an oven for drying at the temperature of about 60 ℃ for more than 12 h; after drying, the ceramic powder is respectively sieved by a 40-mesh sieve and a 80-mesh sieve. In the step S3, the pre-sintering temperature is 900 ℃ and the time is 2 h. The step S5 specifically includes the following steps: placing the second ceramic powder obtained by the treatment of the step S4 in a tumbling tank, adding a dispersing agent and a solvent, and then tumbling at the rotating speed of 200 rpm for 20 hours to obtain premixed slurry; then adding a binder and tumbling for 10 hours at the rotating speed of 200 rpm; and then adding a solvent, a binder and a plasticizer, and carrying out ball milling for 12-16 h at the rotating speed of 200 rpm to obtain uniformly mixed casting slurry with the viscosity of 600-800 mPa & s. In the step S6, the linear speed of the casting machine film belt is about 0.20, and the drying temperature is 40 ℃; setting the pressure of the warm isostatic pressing to be 30 MPa, setting the temperature to be 60 ℃, and maintaining the pressure for 5 min; the binder removal sintering is specifically at 400 ℃, and the ceramic sintering temperature is 1200 ℃.
On the other hand, the invention also provides a lead zirconate stannate thick film ceramic material with high breakdown electric field resistance, which is prepared by the preparation method.
The invention adopts a solid phase method to synthesize PLZS powder and is doped with sintering aid B with different doping amounts2O3ZnO glass, and preparing the thickness-controllable lead zirconate stannate thick film ceramic by a tape casting process. The pre-sintered powder obtained by X-ray diffraction (XRD) is of a perovskite structure, and the sintered crystal grains of the sample are uniformly and compactly distributed and have the size of about 1-2 mu m when observed by a scanning electron microscope. At room temperature, the electric hysteresis loop of the sample changes from an antiferroelectric phase to a ferroelectric phase along with the increase of the electric field, and the composition of the sample is proved to be in a PLZS antiferroelectric phase region.
And calculating the energy storage density and the energy storage efficiency of each sample according to the obtained electric hysteresis loop, so that the ceramic sample can bear higher electric field intensity under the condition of low glass doping amount of PLZS, and higher energy storage density and energy storage efficiency can be obtained. At 0.10 wt% BZ and 0.25 wt% BZ loadings, the samples were able to withstand 560 kV/cm and 685 kV/cm electric fields, respectively, without breakdown. By adding the glass sintering aid for sintering, the glass with a relatively low melting point can form a liquid phase firstly to wrap the crystal grains. According to the liquid phase sintering mechanism, the force exerted by the wet liquid phase and the nucleation rearrangement mechanism result in densification of the solid phase and reduce defects in the sample. The thick film ceramic has the advantages of small size and good compatibility with an integrated circuit, and meanwhile, if the glass sintering aid is added for sintering, the density of the thick film ceramic is increased, so that the thick film ceramic with high breakdown-resistant electric field and high energy storage density is finally formed, and the thick film ceramic has great significance for the practical application of the antiferroelectric/ferroelectric ceramic in the technical field of pulse power.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is a more detailed description of the present invention that is presented in conjunction with specific embodiments, and the practice of the invention is not to be considered limited to those descriptions. It will be apparent to those skilled in the art that a number of simple derivations or substitutions can be made without departing from the inventive concept.
Claims (9)
1. A preparation method of a lead zirconate stannate thick film ceramic material with high breakdown electric field resistance is characterized by comprising the following steps:
step S1: PbO, La2O3、ZrO2、SnO2Weighing and placing the mixture in a nylon ball milling tank according to a preset stoichiometric ratio, adding excessive 3 wt% of PbO, and carrying out ball milling to obtain a first product;
step S2: drying and sieving the first product to obtain first ceramic powder;
step S3: pre-sintering the first ceramic powder in a muffle furnace, and then pre-sintering the first ceramic powder B2O3-the ZnO glass powder is respectively doped into the pre-sintered first ceramic powder according to different mass fractions;
step S4: performing secondary ball milling, drying and sieving to obtain second ceramic powder;
step S5: placing the second ceramic powder in a tumbling tank, adding a dispersing agent and a solvent for tumbling to obtain premixed slurry, adding a binder for continuous tumbling, adding the solvent, the binder and the plasticizer for continuous tumbling to obtain casting slurry;
step S6: and carrying out tape casting molding on the tape casting slurry through a tape casting machine, and obtaining the lead zirconate stannate thick film ceramic material with high breakdown electric field resistance after carrying out isostatic pressing and binder removal sintering.
2. The method for preparing the lead zirconate stannate thick film ceramic material with high breakdown electric field resistance as claimed in claim 1, wherein the ball milling in the step S1 and the step S4 is as follows:
the ball milling medium is zirconium dioxide balls with the diameter of 3mm and 5mm, and the mass ratio is about 3: 2; adopting wet ball milling, and adding a proper amount of alcohol, wherein the raw materials comprise: alcohol: zirconium balls = 1: 2: 5; and (3) ball milling is carried out by adopting a common planetary ball mill, the rotating speed is set to be 250 r/min, and the ball milling time is 24 h.
3. The method for preparing the lead zirconate stannate thick film ceramic material with high breakdown electric field resistance as claimed in claim 1, wherein the drying and screening steps in step S2 and step S4 are as follows:
putting the ball-milled ceramic powder into an oven for drying at the temperature of about 60 ℃ for more than 12 h; after drying, the ceramic powder is respectively sieved by a 40-mesh sieve and a 80-mesh sieve.
4. The method for preparing the lead zirconate stannate thick film ceramic material with high breakdown field resistance as claimed in claim 1, wherein in step S3, the pre-sintering temperature is 900 ℃ and the time is 2 h.
5. The method for preparing the lead zirconate stannate thick film ceramic material with high breakdown electric field resistance as claimed in claim 1, wherein the step S5 comprises the following steps:
placing the second ceramic powder obtained by the treatment of the step S4 in a tumbling tank, adding a dispersing agent and a solvent, and then tumbling at the rotating speed of 200 rpm for 20 hours to obtain premixed slurry; then adding a binder and tumbling for 10 hours at the rotating speed of 200 rpm; and then adding a solvent, a binder and a plasticizer, and carrying out ball milling for 12-16 h at the rotating speed of 200 rpm to obtain uniformly mixed casting slurry with the viscosity of 600-800 mPa & s.
6. The method for preparing a lead zirconate stannate thick film ceramic material with high breakdown field resistance as claimed in claim 1, wherein in step S6, the tape linear speed of the casting machine is about 0.20, and the drying temperature is 40 ℃.
7. The method for preparing a lead zirconate stannate thick film ceramic material with high breakdown electric field resistance as claimed in claim 1, wherein in step S6, the pressure of the isostatic pressing is set to 30 MPa, the temperature is set to 60 ℃, and the pressure holding time is 5 min.
8. The method for preparing a lead zirconate stannate thick film ceramic material with high breakdown field resistance as claimed in claim 1, wherein in step S6, the binder removal sintering is specifically at 400 ℃ and the ceramic sintering temperature is 1200 ℃.
9. The lead zirconate stannate thick film ceramic material with high breakdown electric field resistance is prepared by the preparation method of any one of claims 1 to 8.
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