CN108409319B - Lead-free ceramic material with high energy storage density and charge-discharge performance and preparation method thereof - Google Patents

Lead-free ceramic material with high energy storage density and charge-discharge performance and preparation method thereof Download PDF

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CN108409319B
CN108409319B CN201810184288.0A CN201810184288A CN108409319B CN 108409319 B CN108409319 B CN 108409319B CN 201810184288 A CN201810184288 A CN 201810184288A CN 108409319 B CN108409319 B CN 108409319B
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翟继卫
李峰
沈波
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Tongji University
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Abstract

The invention relates to a lead-free ceramic material with high energy storage density and charge-discharge performance and a preparation method thereof, wherein the ceramic comprises (1-x) BaTiO3‑x(Bi0.9Na0.1)(In1‑yZry)O3(x is more than or equal to 0 and less than or equal to 0.2, and y is more than or equal to 0.1 and less than or equal to 0.3), and the ceramic is obtained by a common sintering method. Compared with a lead-based antiferroelectric material, the material disclosed by the invention does not contain lead, and is an environment-friendly material. Compared with antiferroelectric materials, the system disclosed by the invention has very large energy storage density, current density and power density, and has charge and discharge time of submicrosecond level. This characteristic is greatly advantageous for pulsed capacitor applications. The material has simple manufacturing process and excellent charge and discharge performance, and is suitable for being applied to high-voltage pulse capacitors requiring energy storage and charge and discharge characteristics.

Description

Lead-free ceramic material with high energy storage density and charge-discharge performance and preparation method thereof
Technical Field
The invention belongs to the technical field of functional ceramic materials, and particularly relates to a lead-free ceramic material with high energy storage density and charge-discharge performance and a preparation method thereof.
Background
The pulse capacitor can store the charged energy of a low-power supply to the capacitor within a long time interval, and quickly release the stored energy within a very short time interval at a required moment to form strong current and power. With the continuous development of accelerators, lasers, electron beams, etc., the demand of people for high-voltage pulse large-current generators is increasing. Although a battery has a high energy density, its power density tends to be low because carriers therein move slowly. Dielectric capacitors, although not very high in energy density, are very power dense and can discharge charge in a short time, and are therefore used to generate pulsed voltages and currents.
Materials currently used as pulse capacitors are mainly classified into three types: linear dielectric materials, ferroelectric materials and lead-based antiferroelectric materials. When the applied electric field is larger than that of the antiferroelectric-ferroelectric transition, the antiferroelectric material forms a double ferroelectric hysteresis loop, the electric displacement and the dielectric constant of the material are sharply increased, and the material is in a charged state. When the electric field is removed, the ferroelectric phase induced by the electric field returns to the original antiferroelectric state, and the material is in a discharge state. Because the dipoles in the antiferroelectric material are arranged in an opposite direction, the stored charges can be completely released, so the energy storage density and the energy storage efficiency of the antiferroelectric material are generally higher, and the lead-based antiferroelectric ceramic is a focus of research in the current energy storage materials. The work of the institute for silicone salt of shanghai, cheng hong, liu zheng, the task group of the xian university for slow-rise teacher, has been done in this regard. However, lead-based antiferroelectric materials suffer from several problems: 1. the lead-based antiferroelectric material contains toxic Pb, and causes environmental pollution in the manufacturing and production processes. 2. The lead-based antiferroelectric ceramic has a low Curie temperature, and when the temperature exceeds the Curie temperature, the energy storage density, the current density and the power density of the lead-based antiferroelectric ceramic are greatly reduced, so that the temperature dependence of the lead-based antiferroelectric ceramic is strong. 3. The antiferroelectric-ferroelectric transition electric field of the antiferroelectric material is generally large, which results in a decrease in the cycle life of the capacitor.
The relaxed ceramic material has dielectric dispersion characteristics, i.e., the dielectric constant of the material does not change significantly over a wide temperature range, and the dependence of the stored energy density on temperature is reduced. BaTiO is studied by the Wangxiao Huiyi topic group of Qinghua university3The energy storage property of the material is improved by adding BiYO3The second component is used for adjusting the relaxation performance of the second component so as to optimize the energy storage characteristic of the second component. In 0.91BaTiO3-0.09BiYO3In the system, the energy storage density reaches 0.71J/cm3. The L.X.Xia subject group of Tianjin university passes at Ba1-xSm2x/3Zr0.15Ti0.85O3In the system, Sm is used for replacing Ba ions at the A position to adjust the relaxation performance of the system, and when x is 0.03, the energy storage density of the system reaches a maximum value of 1.13J/cm3. Shanghai institute for silicate researchThe research team also studied the energy storage effect of barium titanate-based ceramics. In (Ba)0.85Ca0.15)(Zr0.10Ti0.90)O3In the system, complex ions (Ni)1/3Nb2/3)4+To replace the B-site ion of the system, thereby optimizing the energy storage effect of the system. When (Ni)1/ 3Nb2/3)4+When the mole fraction of the ions is 30 percent, the energy storage density reaches the maximum value of 0.66J/cm3. In summary, the energy storage effect with respect to barium titanate-based materials is also relatively low. In addition, the research work of barium titanate energy storage materials mainly focuses on improving the energy storage density of the barium titanate energy storage materials, but the charge-discharge characteristics of barium titanate-based relaxor ferroelectric ceramics are rarely reported at present.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a lead-free ceramic material with high energy storage density and charge-discharge performance and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the lead-free ceramic material with high energy storage density and charge-discharge performance comprises the following chemical components: (1-x) BaTiO3-x(Bi0.9Na0.1)(In1-yZry)O3Wherein x is more than or equal to 0 and less than or equal to 0.2, and y is more than or equal to 0.1 and less than or equal to 0.3.
In a preferred embodiment, x is 0.1 and y is 0.2. Under the proportion, the breakdown field strength of the material is optimized, and at the moment, the electric hysteresis loop becomes fine and keeps higher maximum polarization strength and very low residual polarization strength, so that the energy storage density is maximized.
The preparation method of the lead-free ceramic material with high energy storage density and charge-discharge performance comprises the following steps:
(1) selecting BaCO with purity of more than 99%3,TiO2，Bi2O3，Na2CO3，In2O3，ZrO2As a raw material for lead-free ceramics;
(2) weighing materials according to chemical compositions, adding a ball milling medium for ball milling, discharging and drying;
(3) calcining the dried powder in a muffle furnace at 850-1000 ℃ for 1-5 h, taking out the calcined powder, grinding the calcined powder again by using a mortar, and performing secondary calcination after the calcination is finished, wherein the heat preservation time and the temperature are the same as those of the first calcination;
(4) performing secondary ball milling on the calcined powder, discharging, drying, adding PVA for granulation, and pressing under the pressure of 4-8 MPa to prepare a ceramic wafer;
(5) removing glue from the obtained ceramic blank in a muffle furnace, and preserving heat for 5-10 h at 500-600 ℃;
(6) and sintering the ceramic blank after removing the glue at 1200-1300 ℃, controlling the heating rate to be 2-5 ℃/min, preserving the heat at the highest temperature for 2-5 h, naturally cooling to the room temperature, and polishing the sintered ceramic wafer by using abrasive paper with different particle sizes to obtain the thin ceramic wafer with a bright and smooth surface.
And performing ball milling twice in a planetary ball mill, and adding zirconium dioxide beads and absolute ethyl alcohol as ball milling media.
And (3) in the step (2), the ball milling time is 6-8 hours, in the step (4), the ball milling time is 8-12 hours, and the powder is dried in a blast drying oven, wherein the temperature is controlled at 100-120 ℃. And (4) adding 5 wt% of PVA during granulation.
The method further comprises the steps of coating high-temperature silver paste on the front surface and the back surface of the polished ceramic chip, burning the silver in a muffle furnace, and preserving heat for 0.5-1 hour at the temperature of 500-600 ℃.
Compared with the prior art, the material does not contain Pb, does not cause harm to the environment in the processes of production, use and abandonment, and is an environment-friendly energy storage and capacitor material. Meanwhile, because the selected components have dielectric dispersion characteristics, the energy storage density has better temperature stability, particularly, the energy storage density still has excellent charge and discharge performance at room temperature and reaches 1.33J/cm3And the current density and the power density are respectively as high as 659A/cm2And 33MW/cm3(room temperature). More importantly, 90% of energy stored by the intrinsic structure and the nanometer micro-area structure of the material can be released within the time of submicroseconds, so that the performance of the lead-based antiferroelectric ceramic is higher than that of the reported lead-based antiferroelectric ceramicPorcelain and other relaxed ceramic materials.
Drawings
FIG. 1 shows 0.9BaTiO lead-free ceramic material obtained in example 13-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3XRD pattern (SEM figure with the composition attached);
FIG. 2 is 0.9BaTiO lead-free ceramic material prepared in example 23-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3The medium temperature map of (a);
FIG. 3 shows 0.9BaTiO lead-free ceramic material obtained in example 33-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3The electric hysteresis loop of (1);
FIG. 4 shows 0.9BaTiO lead-free ceramic material obtained in example 43-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Under-damped state of time-current change curves at different temperatures.
FIG. 5 shows 0.9BaTiO lead-free ceramic material obtained in example 53-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Time-current change curves at different temperatures in the over-damping state;
FIG. 6 shows 0.9BaTiO lead-free ceramic material obtained in example 53-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Is shown as a graph of energy storage density versus discharge time.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The preparation method of the lead-free ceramic material with high energy storage density and charge-discharge performance comprises the following steps:
(1) selecting a Chinese medicine reagent BaCO with the purity of more than 99 percent3,TiO2，Bi2O3，Na2CO3，In2O3，ZrO2As a raw material for lead-free ceramic materials. According to the chemical formula 0.9BaTiO3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Weighing, adding absolute ethyl alcohol and zirconium dioxide balls into a nylon tank for ball milling, discharging and drying. The ball milling time is 8 hours, and the drying temperature is 120 ℃. And (3) putting the dried powder into a corundum crucible, covering a crucible cover after compacting, putting the corundum crucible into a muffle furnace for calcining, heating to 950 ℃ at the speed of 5 ℃/min, preserving heat for 3 hours, cooling to room temperature, taking out, grinding by using a mortar, and calcining in the corundum crucible again at the same temperature rise rate and heat preservation time as the first time.
(2) And (2) performing secondary ball milling on the synthesized powder obtained in the step (1), discharging and drying. The drying temperature is the same as that in the step (1), and the ball milling time is 12 hours. And adding a proper amount of 5% PVA into the dried powder for granulation, and performing compression molding under the pressure of 4MPa to obtain a ceramic wafer with the diameter of 10mm and the thickness of 1 mm.
(3) And (3) placing the ceramic blank obtained in the step (2) into a muffle furnace for glue removal, heating to 550 ℃ at the speed of 2 ℃/min, and then preserving heat for 10 hours.
(4) And (4) sintering the ceramic blank after the glue is removed, which is obtained in the step (3), at the temperature of 1260 ℃, wherein the heating speed is 3 ℃/min, and the temperature is kept at the highest temperature for 3 hours. And then naturally cooling to room temperature to obtain the barium titanate-based lead-free ceramic material.
(5) And grinding the sintered ceramic wafer into powder by using a mortar, and then carrying out XRD (X-ray diffraction) test at a scanning speed of 5 degrees/min.
And wiping the fired ceramic wafer with absolute ethyl alcohol, and spraying gold to perform SEM test.
FIG. 1 is a 0.9BaTiO lead-free ceramic material obtained in example 13-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3The XRD diffraction pattern of the compound is shown in figure 1, and the phase structures are all shown to be single ABO3And (5) structure. The SEM picture with the component inside shows that the prepared ceramic chip has compact structure, no air holes and grain size of about 0.8 micron.
Example 2
The preparation method of the lead-free ceramic material with high energy storage density and charge-discharge performance comprises the following steps:
(1) selecting a Chinese medicine reagent BaCO with the purity of more than 99 percent3,TiO2，Bi2O3，Na2CO3，In2O3，ZrO2As a raw material for lead-free ceramic materials. According to the chemical formula 0.9BaTiO3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Weighing, adding absolute ethyl alcohol and zirconium dioxide balls into a nylon tank for ball milling, discharging and drying. The ball milling time is 8 hours, and the drying temperature is 120 ℃. And (3) putting the dried powder into a corundum crucible, covering a crucible cover after compacting, putting the corundum crucible into a muffle furnace for calcining, heating to 950 ℃ at the speed of 5 ℃/min, preserving heat for 2 hours, cooling to room temperature, taking out, grinding by using a mortar, and calcining in the corundum crucible again at the same temperature rise rate and heat preservation time as the first time.
(2) And (2) performing secondary ball milling on the synthesized powder obtained in the step (1), discharging and drying. The drying temperature is the same as that in the step (1), and the ball milling time is 12 hours. And adding a proper amount of 5% PVA into the dried powder for granulation, and performing compression molding under the pressure of 4MPa to obtain a ceramic wafer with the diameter of 10mm and the thickness of 1 mm.
(3) And (3) placing the ceramic blank obtained in the step (2) into a muffle furnace for glue removal, heating to 550 ℃ at the speed of 2 ℃/min, and then preserving heat for 10 hours.
(4) And (4) sintering the ceramic blank after the glue is removed, which is obtained in the step (3), at the temperature of 1260 ℃, wherein the heating speed is 3 ℃/min, and the temperature is kept at the highest temperature for 3 hours. And then naturally cooling to room temperature to obtain the barium titanate-based lead-free relaxation ferroelectric ceramic.
(5) And (4) polishing the sintered ceramic wafer obtained in the step (4) by using abrasive paper with different particle sizes to obtain a ceramic slice with a bright and flat surface. High-temperature silver paste is uniformly coated on two sides of the ceramic, then the ceramic is placed into a muffle furnace for glue discharging, and the temperature is raised to 600 ℃ at the speed of 5 ℃/min and then the ceramic is kept for half an hour.
And after the polarization is finished, cleaning the ceramic wafer by using absolute ethyl alcohol, and then testing the ceramic wafer by placing the ceramic wafer into a dielectric temperature spectrum.
FIG. 2 is 0.9BaTiO lead-free ceramic material after polarization prepared in example 23-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3The dielectric temperature spectrum of (1). It can be seen from the figure that the Curie temperature of the system is modulated to around room temperature, which is advantageous for increasing the polarization strength of the system.
Example 3
The preparation method of the lead-free ceramic material with high energy storage density and charge-discharge performance comprises the following steps:
(1) selecting a Chinese medicine reagent BaCO with the purity of more than 99 percent3,TiO2，Bi2O3，Na2CO3，In2O3，ZrO2As a raw material for lead-free ceramic materials. According to the chemical formula 0.9BaTiO3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Weighing, adding absolute ethyl alcohol and zirconium dioxide balls into a nylon tank for ball milling, discharging and drying. The ball milling time is 8 hours, and the drying temperature is 120 ℃. And (3) putting the dried powder into a corundum crucible, covering a crucible cover after compacting, putting the corundum crucible into a muffle furnace for calcining, heating to 950 ℃ at the speed of 5 ℃/min, preserving heat for 3 hours, cooling to room temperature, taking out, grinding by using a mortar, and calcining in the corundum crucible again at the same temperature rise rate and heat preservation time as the first time.
(2) And (2) performing secondary ball milling on the synthesized powder obtained in the step (1), discharging and drying. The drying temperature is the same as that in the step (1), and the ball milling time is 12 hours. And adding a proper amount of 5% PVA into the dried powder for granulation, and performing compression molding under the pressure of 4MPa to obtain a ceramic wafer with the diameter of 10mm and the thickness of 1 mm.
(3) And (3) placing the ceramic blank obtained in the step (2) into a muffle furnace for glue removal, heating to 550 ℃ at the speed of 2 ℃/min, and then preserving heat for 10 hours.
(4) And (4) sintering the ceramic blank after the glue is removed, which is obtained in the step (3), at the temperature of 1260 ℃, wherein the heating speed is 3 ℃/min, and the temperature is kept at the highest temperature for 3 hours. And then naturally cooling to room temperature to obtain the barium titanate-based lead-free relaxation ferroelectric ceramic.
(5) And (4) polishing the sintered ceramic wafer obtained in the step (4) by using abrasive paper with different particle sizes to obtain a ceramic slice with a bright and flat surface. And (3) uniformly coating high-temperature silver paste on two surfaces of the ceramic, then placing the ceramic into a muffle furnace for glue discharging, heating to 600 ℃ at a speed of 5 ℃/min, then preserving the heat for half an hour, cooling to room temperature, and taking out a sample for ferroelectric property test.
FIG. 3 is 0.9BaTiO lead-free ceramic material obtained in example 33-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3The electric hysteresis loop P-E becomes very fine, the maximum polarization intensity keeps a larger value, and the residual polarization intensity is close to zero, so that the energy storage characteristic of the material is favorably improved.
Example 4
The preparation method of the lead-free ceramic material with high energy storage density and charge-discharge performance comprises the following steps:
(1) selecting a Chinese medicine reagent BaCO with the purity of more than 99 percent3,TiO2，Bi2O3，Na2CO3，In2O3，ZrO2As a raw material for lead-free ceramic materials. According to the chemical formula 0.9BaTiO3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Weighing, adding absolute ethyl alcohol and zirconium dioxide balls into a nylon tank for ball milling, discharging and drying. The ball milling time is 8 hours, and the drying temperature is 120 ℃. And (3) putting the dried powder into a corundum crucible, covering a crucible cover after compacting, putting the corundum crucible into a muffle furnace for calcining, heating to 950 ℃ at the speed of 5 ℃/min, preserving heat for 3 hours, cooling to room temperature, taking out, grinding by using a mortar, and calcining in the corundum crucible again at the same temperature rise rate and heat preservation time as the first time.
(2) And (2) performing secondary ball milling on the synthesized powder obtained in the step (1), discharging and drying. The drying temperature is the same as that in the step (1), and the ball milling time is 12 hours. And adding a proper amount of 5% PVA into the dried powder for granulation, and performing compression molding under the pressure of 4MPa to obtain a ceramic wafer with the diameter of 10mm and the thickness of 1 mm.
(3) And (3) placing the ceramic blank obtained in the step (2) into a muffle furnace for glue removal, heating to 550 ℃ at the speed of 2 ℃/min, and then preserving heat for 10 hours.
(4) And (4) sintering the ceramic blank after the glue is removed, which is obtained in the step (3), at the temperature of 1260 ℃, wherein the heating speed is 3 ℃/min, and the temperature is kept at the highest temperature for 3 hours. And then naturally cooling to room temperature to obtain the barium titanate-based lead-free relaxation ferroelectric ceramic.
(5) And (4) polishing the sintered ceramic wafer obtained in the step (4) by using abrasive paper with different particle sizes to obtain a ceramic slice with a bright and flat surface. The diameter and the thickness of the polished ceramic wafer are respectively 4mm and 0.4 mm. And (3) uniformly coating high-temperature silver paste on two surfaces of the ceramic, then putting the ceramic into a muffle furnace for rubber removal, heating to 600 ℃ at a speed of 5 ℃/min, then preserving the heat for half an hour, cooling to room temperature, and taking out a sample for charge and discharge performance test.
FIG. 4 is 0.9BaTiO lead-free ceramic material prepared in example 4 under the action of 10kV/mm electric field3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Current-time (current-time) diagram in the under-damped state. From the oscillation curve, most of energy is released in a short time, so that the charge and discharge performance of the material is improved.
Example 5
The preparation method of the lead-free ceramic material with high energy storage density and charge-discharge performance comprises the following steps:
(1) selecting a Chinese medicine reagent BaCO with the purity of more than 99 percent3,TiO2，Bi2O3，Na2CO3，In2O3，ZrO2As a raw material for lead-free ceramic materials. According to the chemical formula 0.9BaTiO3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3Weighing, adding absolute ethyl alcohol and zirconium dioxide balls into a nylon tank for ball milling, discharging and drying. The ball milling time is 8 hours, and the drying temperature is 120 ℃. The dried powder is filled into a corundum crucibleIn the crucible, after being compacted, the crucible cover is covered, the crucible is placed into a muffle furnace for calcination, the temperature is raised to 950 ℃ at the speed of 5 ℃/min, the temperature is kept for 3 hours, the crucible is taken out after being cooled to the room temperature and is ground by a mortar, and the corundum crucible is calcined again by the method, wherein the temperature raising speed and the temperature keeping time are the same as those of the first time.
(2) And (2) performing secondary ball milling on the synthesized powder obtained in the step (1), discharging and drying. The drying temperature is the same as that in the step (1), and the ball milling time is 12 hours. And adding a proper amount of 5% PVA into the dried powder for granulation, and performing compression molding under the pressure of 4MPa to obtain a ceramic wafer with the diameter of 10mm and the thickness of 1 mm.
(3) And (3) placing the ceramic blank obtained in the step (2) into a muffle furnace for glue removal, heating to 550 ℃ at the speed of 2 ℃/min, and then preserving heat for 10 hours.
(4) And (4) sintering the ceramic blank after the glue is removed, which is obtained in the step (3), at the temperature of 1260 ℃, wherein the heating speed is 3 ℃/min, and the temperature is kept at the highest temperature for 3 hours. And then naturally cooling to room temperature to obtain the barium titanate-based lead-free relaxation ferroelectric ceramic.
(5) And (4) polishing the sintered ceramic wafer obtained in the step (4) by using abrasive paper with different particle sizes to obtain a ceramic slice with a bright and flat surface. The diameter and the thickness of the polished ceramic wafer are respectively 4mm and 0.4 mm. And (3) uniformly coating high-temperature silver paste on two surfaces of the ceramic, then putting the ceramic into a muffle furnace for rubber removal, heating to 600 ℃ at a speed of 5 ℃/min, then preserving the heat for half an hour, cooling to room temperature, and taking out a sample for charge and discharge performance test. In the RLC circuit, a Dahongpao resistor with the resistance value of 275 omega is selected to test the charge-discharge state under over-damping.
FIGS. 5 and 6 show the lead-free ceramic material 0.9BaTiO prepared in example 5 under the action of 10kV/mm electric field3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3A current-time graph in an over-damping state and a change diagram of energy storage density along with discharge time. By the formula wd=R∫1(t)2dt/V gives the energy storage density WdSchematic of the change over time. From this we see that 90% of the charge is fully discharged in a very short time (as indicated by the dashed line) around 0.185 mus, which is a great advantageGenerating instantaneous large current, which is beneficial to the application of high-voltage pulse capacitor.
TABLE 1
Figure BDA0001589786180000081
Table 1 shows the comparison of energy storage and charge and discharge performance between the system of the present invention and the antiferroelectric system, from which it can be seen that the barium titanate-based system of the present invention has higher energy storage current density and power density than the lead-based antiferroelectric system, and is advantageous for the application of the pulse capacitor.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (7)

1. The lead-free ceramic material with high energy storage density and charge-discharge performance is characterized by comprising the following chemical components: 0.9BaTiO3-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3。
2. The method for preparing the lead-free ceramic material with high energy storage density and charge-discharge performance according to claim 1, wherein the method comprises the following steps:
(1) selecting BaCO with purity of more than 99%3,TiO2，Bi2O3，Na2CO3，In2O3，ZrO2As a raw material for lead-free ceramics;
(2) weighing materials according to chemical compositions, adding a ball milling medium for ball milling, discharging and drying;
(3) calcining the dried powder in a muffle furnace at 850-1000 ℃ for 1-5 h, taking out the calcined powder, grinding the calcined powder again by using a mortar, and performing secondary calcination after the calcination is finished, wherein the heat preservation time and the temperature are the same as those of the first calcination;
(4) performing secondary ball milling on the calcined powder, discharging, drying, adding PVA for granulation, and pressing under the pressure of 4-8 MPa to prepare a ceramic wafer;
(5) removing glue from the obtained ceramic blank in a muffle furnace, and preserving heat for 5-10 h at 500-600 ℃;
(6) and sintering the ceramic blank after removing the glue at 1200-1300 ℃, controlling the heating rate to be 2-5 ℃/min, preserving the heat at the highest temperature for 2-5 h, naturally cooling to the room temperature, and polishing the sintered ceramic wafer by using abrasive paper with different particle sizes to obtain the thin ceramic wafer with a bright and smooth surface.
3. The method for preparing the lead-free ceramic material with high energy storage density and charge and discharge performance as claimed in claim 2, wherein the ball milling is carried out in a planetary ball mill for two times, and zirconium dioxide beads and absolute ethyl alcohol are added as ball milling media.
4. The method for preparing the lead-free ceramic material with high energy storage density and charge-discharge performance according to claim 2, wherein the ball milling time in the step (2) is 6-8 hours, and the ball milling time in the step (4) is 8-12 hours.
5. The method for preparing the lead-free ceramic material with high energy storage density and charge-discharge performance according to claim 2, wherein the powder materials obtained in the steps (2) and (4) are dried in a forced air drying oven, and the temperature is controlled to be 100-120 ℃.
6. The method for preparing the lead-free ceramic material with high energy storage density and charge-discharge performance as claimed in claim 2, wherein 5 wt% of PVA is added during granulation in the step (4).
7. The method for preparing the lead-free ceramic material with high energy storage density and charge and discharge performance according to claim 2, further comprising coating high-temperature silver paste on the front surface and the back surface of the polished ceramic chip, burning the silver in a muffle furnace, and preserving the heat at 500-600 ℃ for 0.5-1 hour.
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