A ceramic material, a ceramic component, and a preparation method of the ceramic material and the ceramic component

Abstract

The present invention discloses an antiferroelectric-ferroelectric-ferroelectric ternary solid solution ceramic material, and the chemical formula of the ceramic material is: (1-x-y)PbZrO3-xLaScO3-yBiScO3, where x + y ≤ 0.7 and 0 < x ≤ 0.3. By adding LaScO3 and BiScO3 materials and controlling the doping amounts of the above two, the antiferroelectric-ferroelectric phase transition field can be adjusted within a larger range. When the electric field increases to the antiferroelectric-ferroelectric transition electric field, the polarization intensity rises rapidly, thereby causing the effective energy storage density to increase sharply, and improving the capacitance and energy storage performance of the capacitor material.

Description

Technical Field

[0001] The present invention relates to the field of ceramic materials, in particular to a solid solution ceramic material, and more particularly to an antiferroelectric-ferroelectric-ferroelectric ternary solid solution ceramic material, a ceramic component, and a preparation method of the above ceramic material and ceramic component. Background Art

[0002] In order to meet the increasing significant demands for high-voltage pulse high-current generators in the fields of nuclear physics, electron beams, accelerators, lasers, etc., in recent years, energy storage capacitors have shown a development trend of miniaturization, integration, modularization, and high reliability. Among them, capacitors with antiferroelectric ceramic materials as dielectrics are considered to have unique advantages in the above fields with strict requirements for device miniaturization and reliability due to their high energy storage density, stable performance, strong anti-electromagnetic interference ability, etc., and are ideal materials for preparing energy storage capacitors.

[0003] Currently, commercially used dielectric capacitors are mainly made of dielectric polymers or dielectric ceramics, and their energy density is approximately 10 -2 ~10 -1 Wh / kg (less than 2 J / cm 3 ). Compared with traditional dielectric capacitors, electrochemical supercapacitors have a moderate energy density, but their power density still cannot meet the application requirements of ultra-high power devices and systems such as hybrid electric vehicles and electron guns. Therefore, if the energy storage density of dielectric capacitors can be increased to the level of electrochemical supercapacitors or even batteries, their application fields will be greatly expanded. Dielectric capacitors with high energy storage density will further promote the development of electronic and electrical systems towards miniaturization, lightweight, and integration. At the same time, ceramic dielectric capacitors have good mechanical and thermal properties and are the most critical energy storage components in pulsed power technology.

[0004] The research on antiferroelectric ceramic materials can be traced back to the 1950s and 1960s. Due to the relatively high phase transition field strength of lead zirconate (PbZrO3) antiferroelectric ceramics and the inability to excite double electric hysteresis loops at room temperature, antiferroelectric ceramic materials with lead zirconate titanate (Pb(Zr,Ti)O3, PZT) solid solution as the main crystal phase have been developed. These solid solution materials include PZT antiferroelectric ceramic materials with a zirconium-titanium molar ratio near 95 / 5, which can undergo ferroelectric-antiferroelectric phase transitions under certain external conditions such as temperature, stress, and electric field. However, the antiferroelectric phase region of this system is relatively small, and it is extremely easy to not undergo phase transitions due to component deviation during the material synthesis process. In addition, the antiferroelectric phase of PZT95 / 5 material also needs to be transformed into the ferroelectric phase under high temperature and strong electric field, which also restricts the application of this material. Therefore, this binary system is not suitable for making antiferroelectric ceramic energy storage capacitor materials. Summary of the Invention

[0005] The present invention provides a ceramic material that can be used in ceramic energy storage capacitors to solve the problems of low energy density and capacitance of existing capacitor materials. It can maintain a large dielectric constant and capacitance at a relatively high voltage, and at the same time, further increase the breakdown field strength of the capacitor.

[0006] In a first aspect, the present invention provides an antiferroelectric-ferroelectric-paraelectric ternary solid solution ceramic material, and the chemical formula of the ceramic material is: (1 - x - y)PbZrO3 - xLaScO3 - yBiScO3, where x + y ≤ 0.7 and 0 < x ≤ 0.3.

[0007] The antiferroelectric-ferroelectric-paraelectric ternary solid solution ceramic material provided by the present invention is based on antiferroelectric PbZrO3. By adding LaScO3 and BiScO3 materials, the antiferroelectric-ferroelectric phase transition field can be adjusted within a larger range. When the electric field increases to the antiferroelectric-ferroelectric transition electric field, the polarization intensity rises rapidly, resulting in a sharp increase in the effective energy storage density, thereby improving the capacitance and energy storage performance of the capacitor material.

[0008] In a second aspect, the present invention provides a preparation method for an antiferroelectric-ferroelectric-paraelectric ternary solid solution ceramic material, and the method includes the following steps:

[0009] S1. Mix the raw materials of bismuth oxide, lead carbonate, lanthanum oxide, scandium oxide, and zirconium oxide according to the stoichiometric ratio of the ceramic material described in the first aspect, and ball mill after mixing;

[0010] S2. Calcinate the sample at 600 - 900 °C for 2 - 5 hours, then ball mill the calcined powder again, add a binder and mix evenly, and press it into a disc, controlling the disc thickness to be 50 μm - 1 mm;

[0011] S3. Sinter the obtained disc at 1000 - 1500 degrees Celsius for 1 - 4 hours to obtain a sintered ceramic sheet material.

[0012] The present invention designs an antiferroelectric-ferroelectric-paraelectric ternary solid solution. By adopting the above preparation process and adjusting the layer thickness, the rated voltage at the working temperature is located near the antiferroelectric-ferroelectric transition field, improving the relative dielectric constant and breakdown field strength at high voltage, and enhancing the capacitance and energy storage performance of the capacitor material.

[0013] In an optional embodiment, in the above step S2, the thickness of the disc is controlled to be 100 - 800 μm.

[0014] In an optional embodiment, in the above step S2, the calcination temperature is 700 - 850 °C.

[0015] In an alternative embodiment, in the above step S2, the calcination time is 3 - 4 hours.

[0016] In an alternative embodiment, in the above step S3, the sintering temperature is 1100 - 1350 °C.

[0017] In an alternative embodiment, in the above step S3, the sintering time is 2 - 3 hours.

[0018] In a third aspect, the present invention provides a method for preparing a ceramic component, the method comprising, after obtaining the ceramic material described in the second aspect, applying silver to the upper and lower surfaces of the ceramic material and sintering at 700 - 900 °C for 10 - 30 min under a protective atmosphere to obtain the ceramic component.

[0019] In an alternative embodiment, in the above step, the sintering temperature is 800 - 850 °C.

[0020] In an alternative embodiment, in the above step, the sintering time is 10 - 20 min.

[0021] In a fourth aspect, the present invention provides a ceramic component obtained by the preparation method described in the fourth aspect.

[0022] For the preparation method of the ceramic material disclosed in the second aspect above, the preparation method of the ceramic component disclosed in the third aspect, and the possible technical effects that the ceramic component disclosed in the fourth aspect may achieve, please refer to the technical effects that can be achieved by the first aspect or various possible solutions in the first aspect above, and will not be repeated here.

[0023] Other features and advantages of the embodiments of the present application will be described in detail in the subsequent specific implementation part. Specific Embodiments

[0024] In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0025] As mentioned above, the phase transition field strength of traditional lead zirconate (PbZrO3) antiferroelectric ceramics is relatively high, and a double electric hysteresis loop cannot be excited at room temperature. The antiferroelectric ceramic materials with a solid solution of lead zirconate titanate (Pb(Zr,Ti)O3, PZT) as the main crystal phase can undergo ferroelectric-antiferroelectric phase transitions under certain external conditions such as temperature, stress, and electric field. However, the antiferroelectric phase region of this system is relatively small, and it is extremely easy to not undergo a phase transition due to component deviation during the material synthesis process. In addition, the antiferroelectric phase of PZT95 / 5 material also needs to be transformed into a ferroelectric phase under high temperature and strong electric field, which also restricts the application of this kind of material. In addition, when an external electric field acts on antiferroelectric ceramics, there is an antiferroelectric phase-ferroelectric phase transition, which induces a rapid increase in the polarization intensity. When the external electric field is removed, the ferroelectric phase induced by the electric field quickly transforms back into the antiferroelectric phase, resulting in an almost zero remanent polarization intensity. Therefore, only when the breakdown electric field strength of the antiferroelectric ceramic capacitor is higher than the antiferroelectric phase-ferroelectric phase transition electric field strength can a higher energy density be obtained. Therefore, the present technology aims to solve the problems of low energy density and capacitance of existing capacitor materials, and can still maintain a large dielectric constant and capacitance at a higher voltage. At the same time, the breakdown field strength of the capacitor is further improved.

[0026] Based on this, an embodiment of the present invention provides an antiferroelectric-paraelectric-ferroelectric ternary solid solution ceramic material, and the chemical formula of the ceramic material is: (1-x-y)PbZrO3-xLaScO3-yBiScO3, where x + y ≤ 0.7 and 0 < x ≤ 0.3. The applicant is based on the antiferroelectric PbZrO3, and by adding LaScO3 and BiScO3 materials, when the electric field increases to the antiferroelectric-ferroelectric transition electric field, the polarization intensity rises rapidly, resulting in a sharp increase in the effective energy storage density. The antiferroelectric-ferroelectric phase transition conditions can be adjusted within a larger range to improve the material performance, thereby greatly increasing the relative dielectric constant and breakdown field strength under high voltage, and enhancing the dielectric constant, capacitance, and service performance of the capacitor material. The applicant found through experiments that when the content of the paraelectric and ferroelectric materials is controlled such that x + y ≤ 0.7 and x ≤ 0.3, the breakdown field strength of the obtained capacitor can be greatly improved, the dielectric constant and energy density under high voltage are enhanced, and at the same time, the capacitance and service performance of the capacitor are also improved.

[0027] To better understand the technical solution provided by the embodiment of the present invention, the following briefly introduces the application scenarios applicable to the technical solution provided by the embodiment of the present invention. It should be noted that the following introduced application scenarios are only used to illustrate the embodiment of the present invention rather than to limit it. In specific implementation, the technical solution provided by the embodiment of the present invention can be flexibly applied according to actual needs.

[0028] After introducing the application scenarios of the embodiments of the present invention, the following further elaborates on the preferred embodiments of the present invention. It should be understood that the preferred embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention. Moreover, without conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other.

[0029] In addition, although the embodiments of the present invention provide method operation steps as shown in the following embodiments, based on routine or non-creative labor, more or fewer operation steps may be included in the method. In steps where there is no necessary causal relationship logically, the execution order of these steps is not limited to the endpoints within the scope disclosed herein, and any values are not limited to the exact range or value. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0030] The following details the preparation method of the ceramic material provided by the embodiments of the present invention.

[0031] A preparation method of an antiferroelectric-ferroelectric-ferroelectric ternary solid solution ceramic material, the method comprising the following steps:

[0032] S1. Prepare raw materials according to the chemical formula (1 - x - y)PbZrO3 - xLaScO3 - yBiScO3 (where x + y ≤ 0.7, 0 < x ≤ 0.3), mix the raw materials of bismuth oxide, lead carbonate, lanthanum oxide, scandium oxide, and zirconium oxide according to the above stoichiometric ratio, and ball mill after mixing;

[0033] S2. Calcinate the sample at 600 - 900 °C for 2 - 5 hours, then ball mill the calcined powder again, add a binder and mix evenly, and press it into a disc, controlling the thickness of the disc to be 50 μm - 1 mm;

[0034] S3. Sinter the obtained disc at 1000 - 1500 degrees Celsius for 1 - 4 hours to obtain the sintered ceramic sheet material.

[0035] In the above-mentioned step S1, the (1-x-y)PbZrO3-xLaScO3-yBiScO3 is a ternary solid solution, in which PbZrO3 with antiferroelectric properties is the main component, and LaScO3 and BiScO3, as paraelectric and ferroelectric materials, are solid-soluted with the antiferroelectric material to form a ternary ceramic solid solution, and x + y ≤ 0.7, 0 < x ≤ 0.3 are satisfied. In the above ball milling process, a dry or wet ball milling process can be adopted. When using the wet ball milling process, anhydrous ethanol is preferably used as the medium. The grinding balls are preferably zirconia, and the specific ball milling equipment is not limited, and the ball milling machinery commonly used in powder engineering can be selected according to needs to achieve the purpose of sufficient reaction of raw materials. The above step uses oxides or carbonates of the above components as raw materials, but it is not limited to this, and corresponding other salts or oxide raw materials can also be used, and the calcination temperature and ball milling parameters can be adjusted accordingly.

[0036] In addition, preferably, after ball milling, there is also a step of drying at 40°C to 90°C for 3 to 5 hours.

[0037] After drying is completed, the sample can be calcined at 600 to 900°C for 2 to 5 hours. The purpose of this step is to exclude the moisture of the raw materials through pre-calcination treatment on the one hand, and to improve the activity of the raw materials on the other hand. By pre-calcining, the composition and microstructure of the raw materials are improved, so that the antiferroelectric body forms a phase and crystallizes in advance, thereby improving the performance of the finished product. The above calcination temperature is preferably 700 to 850°C, and the calcination time is preferably 2 to 3 hours.

[0038] After the pre-calcination process is completed, by re-ball milling the pre-calcined raw materials and controlling the ball milling process parameters, the secondary ball milling can also be realized by dry or wet methods. When using the wet ball milling process, anhydrous ethanol is preferably used as the medium. The grinding balls are also preferably zirconia, and the specific ball milling equipment is not limited. After the secondary ball milling is completed, an adhesive is added, and the adhesive is mixed evenly with the powder. Then, it is pressed into a disc shape by a tablet press, and the thickness of the disc is controlled to be 50μm to 1mm, preferably 100 to 800μm. By adjusting the layer thickness to an appropriate thickness, the rated voltage at the working temperature can be located near the antiferroelectric-ferroelectric transition field. In the above bonding process, PVA and PEG are preferably used as adhesives.

[0039] After obtaining the pressed product, subsequent sintering steps can be carried out. Specifically, the sample can be sintered at 1000 to 1500 degrees Celsius for 1 to 4 hours. The above sintering temperature is preferably 1100 to 1350°C for 2 to 3 hours. The above sintering process can adopt one-stage sintering or multi-stage step-by-step sintering.

[0040] The step-by-step sintering can preferably adopt a three-stage sintering process. The first stage: sinter at 1000 - 1100°C for 0.5 - 1 hour. At this stage, the particles in the raw materials undergo rearrangement, bonding occurs at the contact points, and the voids deform and shrink. The second stage: sinter at 1100 - 1250°C for 1 - 2 hours. At this stage, mass transfer begins, the grain boundaries increase, and the voids further deform and shrink, but still remain connected. The third stage: sinter at 1250 - 1400°C for 2 - 3 hours. At this stage, mass transfer continues, the particles grow, the pores become isolated closed pores, and the density and strength of the product are significantly improved. Through the above three-stage sintering process, the heating and cooling processes can be precisely controlled, the microstructure and properties of the material can be optimized, and the crystallization purity of the ceramic material and the performance stability of the product can be improved.

[0041] In addition, during the sintering process, hot pressing sintering can be adopted. Compared with traditional solid-phase sintering, hot pressing sintering can reduce the sintering temperature, shorten the sintering time, and also has the effect of refining grains. As the grains are refined, the breakdown electric field of the ceramic can be greatly increased. The preferred hot pressing pressure is 1.1 - 1.4t.

[0042] Through the above sintering process, the required antiferroelectric-ferroelectric-paraelectric ternary solid solution ceramic sheet is obtained. Further, by coating silver on the upper and lower surfaces of the ceramic material and sintering at 700 - 900°C for 10 - 30 min under a protective atmosphere, a ceramic capacitor capable of being used for energy storage is obtained. To further control the performance of the capacitor, the above sintering temperature and time are preferably 800 - 850°C and 10 - 20 min.

[0043] The above-mentioned method of using solid-phase sintering to prepare the ternary solid solution ceramic material and the ceramic capacitor is mentioned, but the present invention is not limited to obtaining them using the solid-phase sintering process. Using plasma discharge sintering also belongs to one of the preferred methods for preparing the above materials. The discharge plasma generated by the DC pulse current is used to cause the powder to heat itself and activate the surface, achieving the heating effect, and combining the two factors of heating and pressing that can promote sintering, which can greatly improve the relative density of the prepared ceramic, can accelerate the heating rate, reduce the sintering temperature and the holding time. Therefore, using plasma discharge sintering can correspondingly shorten the sintering temperature to 800 - 1100°C, shorten the sintering time to 0.5 - 2 hours, and at the same time, only one-stage sintering can be adopted.

[0044] According to the process introduced above, the following representative examples are selected and their relevant properties are tested.

[0045] Example 1:

[0046] S1. Prepare raw materials according to the chemical formula 0.8PbZrO3-0.2BiScO3. Mix the raw materials of bismuth oxide, lead carbonate, scandium oxide, and zirconium oxide according to the above stoichiometric ratio, and use wet ball milling and then pass through a 100-mesh sieve;

[0047] S2. Calcinate the sample at 800 °C for 3 hours. Then, ball mill the calcined powder again and pass through a 200-mesh sieve. Add PVA and PEG as binders and mix evenly, and press into a disc, controlling the disc thickness to be 500 μm;

[0048] S3. Hot press and sinter the obtained disc at 1350 °C for 2 hours, controlling the pressure to be 1.2 t to obtain the sintered ceramic sheet material.

[0049] S4. Brush silver on the upper and lower surfaces of the obtained ceramic sheet material and sinter at 800 °C for 15 min under a protective atmosphere to obtain a ceramic capacitor that can be used for energy storage.

[0050] Test the obtained capacitor material to obtain its energy storage density W (J / cm 3 ), breakdown field strength E (kV / cm), and relative dielectric constant ε.

[0051] Example 2:

[0052] S1. Prepare raw materials according to the chemical formula 0.7PbZrO3-0.1LaScO3-0.2BiScO3. Mix the raw materials of bismuth oxide, lead carbonate, lanthanum oxide, scandium oxide, and zirconium oxide according to the above stoichiometric ratio, and use wet ball milling and then pass through a 100-mesh sieve;

[0053] S2. Calcinate the sample at 800 °C for 3 hours. Then, ball mill the calcined powder again and pass through a 200-mesh sieve. Add PVA and PEG as binders and mix evenly, and press into a disc, controlling the disc thickness to be 500 μm;

[0054] S3. Hot press and sinter the obtained disc at 1350 °C for 2 hours, controlling the pressure to be 1.2 t to obtain the sintered ceramic sheet material.

[0055] S4. Brush silver on the upper and lower surfaces of the obtained ceramic sheet material and sinter at 800 °C for 15 min under a protective atmosphere to obtain a ceramic capacitor that can be used for energy storage.

[0056] Test the obtained capacitor material to obtain its energy storage density W (J / cm 3 ), breakdown field strength E (kV / cm), and relative dielectric constant ε.

[0057] Example 3:

[0058] S1. Prepare raw materials according to the chemical formula 0.6PbZrO3-0.2LaScO3-0.2BiScO3. Mix the raw materials of bismuth oxide, lead carbonate, lanthanum oxide, scandium oxide, and zirconium oxide according to the above stoichiometric ratio, and use wet ball milling followed by passing through a 100-mesh sieve;

[0059] S2. Calcinate the sample at 800 °C for 3 hours. Then, re-ball mill the calcined powder and pass it through a 200-mesh sieve. Add PVA and PEG as binders, mix evenly, and press into a disk, controlling the disk thickness to be 500 μm;

[0060] S3. Hot press and sinter the obtained disk at 1350 °C for 2 hours, controlling the pressure to be 1.2 t to obtain the sintered ceramic sheet material.

[0061] S4. Coat silver on the upper and lower surfaces of the obtained ceramic sheet material and sinter at 800 °C for 15 min under a protective atmosphere to obtain a ceramic capacitor that can be used for energy storage.

[0062] Test the obtained capacitor material to obtain its energy storage density W (J / cm 3 ), breakdown field strength E (kV / cm), and relative dielectric constant ε.

[0063] Example 4:

[0064] S1. Prepare raw materials according to the chemical formula 0.5PbZrO3-0.3LaScO3-0.2BiScO3. Mix the raw materials of bismuth oxide, lead carbonate, lanthanum oxide, scandium oxide, and zirconium oxide according to the above stoichiometric ratio, and use wet ball milling followed by passing through a 100-mesh sieve;

[0065] S2. Calcinate the sample at 800 °C for 3 hours. Then, re-ball mill the calcined powder and pass it through a 200-mesh sieve. Add PVA and PEG as binders, mix evenly, and press into a disk, controlling the disk thickness to be 500 μm;

[0066] S3. Hot press and sinter the obtained disk at 1350 °C for 2 hours, controlling the pressure to be 1.2 t to obtain the sintered ceramic sheet material.

[0067] S4. Coat silver on the upper and lower surfaces of the obtained ceramic sheet material and sinter at 800 °C for 15 min under a protective atmosphere to obtain a ceramic capacitor that can be used for energy storage.

[0068] Test the obtained capacitor material to obtain its energy storage density W (J / cm 3 ), breakdown field strength E (kV / cm), and relative dielectric constant ε.

[0069] Example 5:

[0070] S1. Prepare raw materials according to the chemical formula 0.4PbZrO3 - 0.4LaScO3 - 0.2BiScO3. Mix the raw materials of bismuth oxide, lead carbonate, lanthanum oxide, scandium oxide, and zirconium oxide according to the above stoichiometric ratio, and use wet ball milling followed by passing through a 100-mesh sieve;

[0071] S2. Calcinate the sample at 800 °C for 3 hours. Then, re-ball mill the calcined powder and pass it through a 200-mesh sieve. Add PVA and PEG as binders, mix evenly, and press into a disc, controlling the disc thickness to be 500 μm;

[0072] S3. Hot press and sinter the obtained disc at 1350 °C for 2 hours, controlling the pressure to be 1.2 t to obtain the sintered ceramic sheet material.

[0073] S4. Coat silver on the upper and lower surfaces of the obtained ceramic sheet material and sinter at 800 °C for 15 min under a protective atmosphere to obtain a ceramic capacitor capable of being used for energy storage.

[0074] Test the obtained capacitor material to obtain its energy storage density W (J / cm 3 ), breakdown field strength E (kV / cm), and relative dielectric constant ε.

[0075] Example 6:

[0076] S1. Prepare raw materials according to the chemical formula 0.3PbZrO3 - 0.5LaScO3 - 0.2BiScO3. Mix the raw materials of bismuth oxide, lead carbonate, lanthanum oxide, scandium oxide, and zirconium oxide according to the above stoichiometric ratio, and use wet ball milling followed by passing through a 100-mesh sieve;

[0077] S2. Calcinate the sample at 800 °C for 3 hours. Then, re-ball mill the calcined powder and pass it through a 200-mesh sieve. Add PVA and PEG as binders, mix evenly, and press into a disc, controlling the disc thickness to be 500 μm;

[0078] S3. Hot press and sinter the obtained disc at 1350 °C for 2 hours, controlling the pressure to be 1.2 t to obtain the sintered ceramic sheet material.

[0079] S4. Coat silver on the upper and lower surfaces of the obtained ceramic sheet material and sinter at 800 °C for 15 min under a protective atmosphere to obtain a ceramic capacitor capable of being used for energy storage.

[0080] Test the obtained capacitor material to obtain its energy storage density W (J / cm 3 ), breakdown field strength E (kV / cm), and relative dielectric constant ε.

[0081] The test results of the above examples are as follows in the table:

[0082] Table 1 Capacitor performance obtained in Examples 1-6

[0083] <![CDATA[W (J / cm 3 )]]> Breakdown field strength (kV / cm) Relative dielectric constant ε Example 1 10.2 453 677 Example 2 11.7 456 356 Example 3 13.5 558 301 Example 4 11.4 579 251 Example 5 10.5 516 223 Example 6 7.2 372 198

[0084] As shown in Table 1, through the above Examples 1-6, it can be seen that when paraelectric materials and ferroelectric materials are doped into antiferroelectric PbZrO3, the energy storage density of ceramic capacitors can be significantly improved, and its energy storage density can reach 13.5 J / cm 3 , and the breakdown field strength has also been significantly improved. Moreover, when the doping amount of LaScO3 is controlled below 0.3, the comprehensive performance of the obtained capacitors is the best.

[0085] Example 7:

[0086] S1. Prepare raw materials according to the chemical formula PbZrO3, mix lead carbonate and zirconia raw materials according to the above stoichiometric ratio, and perform wet ball milling and then pass through a 100-mesh sieve;

[0087] S2. Calcinate the sample at 800 °C for 3 hours, then ball mill the calcined powder again and pass through a 200-mesh sieve, add PVA and PEG as binders and mix evenly, and press into a disc, controlling the disc thickness to be 500 μm;

[0088] S3. Hot press and sinter the obtained disc at 1350 °C for 2 hours, controlling the pressure to be 1.2 t to obtain the sintered ceramic sheet material.

[0089] S4. Brush silver on the upper and lower surfaces of the obtained ceramic sheet material and sinter at 800 °C for 15 min under a protective atmosphere to obtain a ceramic capacitor that can be used for energy storage.

[0090] Test the obtained capacitor material to obtain its energy storage density W (J / cm 3 ), breakdown field strength E (kV / cm), and relative permittivity ε.

[0091] Example 8:

[0092] S1. Prepare raw materials according to the chemical formula 0.8PbZrO3-0.2LaScO3, mix lead carbonate, lanthanum oxide, scandium oxide, and zirconia raw materials according to the above stoichiometric ratio, and perform wet ball milling and then pass through a 100-mesh sieve;

[0093] S2. Calcinate the sample at 800 °C for 3 hours, then ball mill the calcined powder again and pass through a 200-mesh sieve, add PVA and PEG as binders and mix evenly, and press into a disc, controlling the disc thickness to be 500 μm;

[0094] S3. Hot press and sinter the obtained disc at 1350 °C for 2 hours, control the pressure at 1.2 t, and obtain the sintered ceramic sheet material.

[0095] S4. Brush silver on the upper and lower surfaces of the obtained ceramic sheet material and sinter it at 800 °C for 15 min under a protective atmosphere to obtain a ceramic capacitor capable of energy storage.

[0096] Test the obtained capacitor material to obtain its energy storage density W (J / cm 3 ), breakdown field strength E (kV / cm), and relative dielectric constant ε.

[0097] Example 9:

[0098] S1. Prepare raw materials according to the chemical formula 0.3PbZrO3 - 0.2LaScO3 - 0.4BiScO3. Mix the raw materials of bismuth oxide, lead carbonate, lanthanum oxide, scandium oxide, and zirconium oxide according to the above stoichiometric ratio, and use wet ball milling and then pass through a 100-mesh sieve.

[0099] S2. Calcinate the sample at 800 °C for 3 hours. Then, ball mill the calcined powder again and pass through a 200-mesh sieve. Add PVA and PEG as binders, mix evenly, and press into a disc, controlling the disc thickness at 500 μm.

[0100] S3. Hot press and sinter the obtained disc at 1350 °C for 2 hours, control the pressure at 1.2 t, and obtain the sintered ceramic sheet material.

[0101] S4. Brush silver on the upper and lower surfaces of the obtained ceramic sheet material and sinter it at 800 °C for 15 min under a protective atmosphere to obtain a ceramic capacitor capable of energy storage.

[0102] Test the obtained capacitor material to obtain its energy storage density W (J / cm 3 ), breakdown field strength E (kV / cm), and relative dielectric constant ε.

[0103] Example 10:

[0104] S1. Prepare raw materials according to the chemical formula 0.3PbZrO3 - 0.2LaScO3 - 0.5BiScO3. Mix the raw materials of bismuth oxide, lead carbonate, lanthanum oxide, scandium oxide, and zirconium oxide according to the above stoichiometric ratio, and use wet ball milling and then pass through a 100-mesh sieve.

[0105] S2. Calcinate the sample at 800 °C for 3 hours. Then, ball mill the calcined powder again and pass through a 200-mesh sieve. Add PVA and PEG as binders, mix evenly, and press into a disc, controlling the disc thickness at 500 μm.

[0106] S3. Hot press and sinter the obtained disc at 1350 °C for 2 hours, control the pressure at 1.2 t, and obtain the sintered ceramic sheet material.

[0107] S4. Coat silver on the upper and lower surfaces of the obtained ceramic sheet material and sinter at 800 °C for 15 min under a protective atmosphere to obtain a ceramic capacitor capable of energy storage.

[0108] Test the obtained capacitor material to obtain its energy storage density W (J / cm 3 ), breakdown field strength E (kV / cm), and relative dielectric constant ε at a 10 kV deflection voltage.

[0109] Example 11:

[0110] S1. Prepare raw materials according to the chemical formula 0.2PbZrO3 - 0.2LaScO3 - 0.6BiScO3. Mix the raw materials of bismuth oxide, lead carbonate, lanthanum oxide, scandium oxide, and zirconium oxide according to the above stoichiometric ratio, and use wet ball milling followed by passing through a 100-mesh sieve.

[0111] S2. Calcinate the sample at 800 °C for 3 hours. Then, re-ball mill the calcined powder and pass it through a 200-mesh sieve. Add PVA and PEG as binders, mix evenly, and press into a disc, controlling the disc thickness at 500 μm.

[0112] S3. Hot press and sinter the obtained disc at 1350 °C for 2 hours, control the pressure at 1.2 t, and obtain the sintered ceramic sheet material.

[0113] S4. Coat silver on the upper and lower surfaces of the obtained ceramic sheet material and sinter at 800 °C for 15 min under a protective atmosphere to obtain a ceramic capacitor capable of energy storage.

[0114] Test the obtained capacitor material to obtain its energy storage density W (J / cm 3 ), breakdown field strength E (kV / cm), and relative dielectric constant ε at a 10 kV deflection voltage.

[0115] The test results of the above embodiments are as follows in the table:

[0116] Table 2 Capacitor performance obtained in Examples 3, 7 - 11

[0117] <![CDATA[W (J / cm 3 )]]> Breakdown field strength (kV / cm) Relative dielectric constant ε Example 7 3.3 231 202 Example 8 9.6 462 196 Example 3 13.5 558 301 Example 9 12.3 480 482 Example 10 10.5 453 524 Example 11 9.6 378 511

[0118] As shown in Table 2, it can be seen from the above embodiments that when paraelectric materials and ferroelectric materials are doped into antiferroelectric PbZrO3, the energy storage density of the ceramic capacitor can be significantly improved, and its energy storage density can reach 13.5 J / cm 3, and the breakdown field strength and relative permittivity have also been significantly improved, and the capacitor can still maintain a large permittivity and capacitance at a relatively high voltage. Moreover, when the total doping content of LaScO3 and BiScO3 is controlled below 0.7, the obtained capacitor has the best comprehensive performance.

[0119] Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications to these embodiments once they learn the basic creative concept. Therefore, the appended claims are intended to be construed to include the preferred embodiments as well as all changes and modifications falling within the scope of the present invention.

[0120] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention is also intended to include these modifications and variations.

Claims

1. An antiferroelectric-paraelectric-ferroelectric ternary solid solution ceramic material, characterized in that: The chemical formula of the ceramic material is: (1-xy)PbZrO3-xLaScO3-yBiScO3, wherein x+y≤0.7, 0.1≤x≤0.

3.

2. A method for preparing the antiferroelectric-paraelectric-ferroelectric ternary solid solution ceramic material according to claim 1, characterized in that: The following steps are involved: S1, mixing bismuth oxide, lead carbonate, lanthanum oxide, scandium oxide and zirconium oxide raw materials according to a stoichiometric ratio, and ball milling the mixed materials; S2, calcining the sample at 600-900 °C for 2-5 hours, then ball-milling the calcined powder again, adding a binder to mix evenly, and pressing it into a disc with a thickness of 50 μm-1 mm; S3, sintering the obtained disc at 1000-1500 degrees Celsius for 1-4 hours to obtain a sintered ceramic sheet material.

3. A method for preparing the antiferroelectric-paraelectric-ferroelectric ternary solid solution ceramic material according to claim 2, characterized in that: In the step S2, the thickness of the disk is controlled to be 100-800 μm.

4. A method for preparing the antiferroelectric-paraelectric-ferroelectric ternary solid solution ceramic material according to claim 2, characterized in that: In the step S2, the calcination temperature is 700-850°C.

5. A method for preparing the antiferroelectric-paraelectric-ferroelectric ternary solid solution ceramic material according to claim 4, characterized in that: In the step S2, the calcination time is 3-4 hours.

6. A method for preparing the antiferroelectric-paraelectric-ferroelectric ternary solid solution ceramic material according to claim 2, characterized in that: In step S3, the sintering temperature is 1100-1350°C.

7. A method for preparing the antiferroelectric-paraelectric-ferroelectric ternary solid solution ceramic material according to claim 6, characterized in that: In step S3, the sintering time is 2-3 hours.

8. A method for preparing a ceramic component, characterized in that: The method comprises: after obtaining the ceramic material according to any one of claims 2 to 7, brushing silver on the upper and lower surfaces of the ceramic material and sintering at 700 to 900° C. for 10 to 30 minutes under a protective atmosphere to obtain the ceramic element.

9. A method for preparing the ceramic element according to claim 8, characterized in that: The sintering temperature under protective atmosphere is 800~850℃.

10. A method for preparing the ceramic element according to claim 8, characterized in that: The sintering time under protective atmosphere is 10~20min.

11. A ceramic component obtained by the preparation method according to any one of claims 8 to 10.