CN110759727A - Lead-free ceramic material with high energy storage and charge-discharge performance and preparation method thereof - Google Patents

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

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CN110759727A
CN110759727A CN201911159286.7A CN201911159286A CN110759727A CN 110759727 A CN110759727 A CN 110759727A CN 201911159286 A CN201911159286 A CN 201911159286A CN 110759727 A CN110759727 A CN 110759727A
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energy storage
ceramic material
charge
lead
high energy
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杨海波
李达
林营
张苗
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

The invention provides a lead-free ceramic material with high energy storage and charge-discharge performance and a preparation method thereof, wherein the chemical formula is as follows: (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3‑xSr(Ti0.85Zr0.15)O3Wherein x is more than or equal to 0.10 and less than or equal to 0.40. The method comprises the following steps: (1) mixing SrCO3、Na2CO3、TiO2、ZrO2And Bi2O3Uniformly mixing to obtain raw material powder, briquetting, presintering, crushing and sieving to obtain presintering powder; (2) ball-milling the pre-sintered powder to obtain raw material powder; (3) and tabletting the raw material powder, and sintering to obtain the ceramic material with high energy storage and charge and discharge performance. The ceramic material has high energy storage performance and excellent charging performanceThe discharge performance is a promising high-performance dielectric candidate material, and has the characteristics of environmental friendliness, high practicability and the like.

Description

Lead-free ceramic material with high energy storage and charge-discharge performance and preparation method thereof
Technical Field
The invention belongs to the field of energy storage ceramics, and particularly relates to a lead-free ceramic material with high energy storage and charge-discharge performance and a preparation method thereof.
Background
With the excessive consumption of non-renewable resources such as fossil fuels, the environmental pollution is becoming serious, the demand of the electronic industry is increasing, and the development of novel renewable environment-friendly energy storage medium materials is becoming more urgent and important. Compared with a lithium ion battery or a fuel battery, the dielectric capacitor has the advantages of high power density, high energy release speed, environmental friendliness and the like, and is widely concerned in the field of advanced energy storage. Polymers and ceramics are the two main materials of dielectric capacitors. Among them, ceramic dielectric materials have received much attention in recent decades due to their excellent mechanical properties, large dielectric constant and temperature stability compared to polymers.
Na0.5Bi0.5TiO3(NBT) -based ceramics are considered to be important candidates for high performance dielectric capacitors due to their environmentally friendly, large saturation polarization, strong ferroelectricity and dielectric properties. But its lower breakdown field strength and greater remanent polarization result in lower energy storage density, which limits their practical application in pulsed power systems.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a lead-free ceramic material with high energy storage and charge-discharge performance and a preparation method thereof.
The invention is realized by the following technical scheme:
a lead-free ceramic material with high energy storage and charge-discharge performance has a chemical formula as follows: (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3Wherein x is more than or equal to 0.10 and less than or equal to 0.40.
Preferably, the energy storage density of the lead-free ceramic material with high energy storage and charge-discharge performance is 2.55-3.13J/cm under the conditions of room temperature and 10Hz frequency3The energy storage efficiency is 82.25% -91.13%; when x is 0.3, the current density is 687.37A/cm under the conditions of room temperature and 120kV/cm electric field intensity2The power density is 41.24MW/cm3The discharge time was 125.6 ns.
The preparation method of the lead-free ceramic material with high energy storage and charge-discharge performance comprises the following steps:
(1) mixing SrCO3、Na2CO3、TiO2、ZrO2And Bi2O3Uniformly mixing to obtain raw material powder, briquetting, presintering to obtain blocky solid, and crushing and sieving the blocky solid to obtain presintering powder;
(2) ball-milling the pre-sintered powder obtained in the step (1) to obtain raw material powder;
(3) and (3) tabletting and molding the raw material powder obtained in the step (2), and sintering to obtain the ceramic material with lead-free high energy storage and charge and discharge performance.
Preferably, in the step (1), the uniform mixing is specifically; and (3) ball milling is carried out by taking absolute ethyl alcohol as a medium, the ball milling time is 20-25 hours, and drying and sieving are carried out after ball milling.
Preferably, in the step (1), the pre-sintering is performed at 850-950 ℃ for 2-6 hours.
Preferably, in the step (2), the medium adopted by ball milling is absolute ethyl alcohol, the ball milling time is 20-25 hours, and drying is carried out after ball milling.
Preferably, in the step (3), the tabletting is specifically performed by a cold isostatic pressing method.
Preferably, the cold isostatic pressing is formed by maintaining pressure at 190-210 MPa for 3-5 minutes.
Preferably, in the step (3), the sintered ceramic is insulated for 2-5 hours at 1200-1280 ℃.
Compared with the prior art, the invention has the following beneficial technical effects:
material (1-x) (Na) of the present invention0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3To (Na)0.5Bi0.5)0.7Sr0.3TiO3As a matrix, by introducing Sr (Ti)0.85Zr0.15)O3Reducing the average grain size of the material, thereby enabling dielectricThe breakdown field strength is significantly enhanced. Cation Zr4+Into the crystal lattice to completely replace B-site Ti4+The ferroelectricity of the material is weakened, and the relaxivity of the material is enhanced, so that the relatively large saturation polarization intensity is kept while the residual polarization intensity of the material is effectively inhibited, and the improvement of the energy storage density and the efficiency are greatly promoted. When the amount of solid solution is more than 0.40mol, the saturation polarization of the ceramic starts to be greatly reduced, resulting in a reduction in the energy storage density, and therefore, the present invention introduces Sr (Ti)0.85Zr0.15)O3And control Sr (Ti)0.85Zr0.15)O3The solid solution amount overcomes the defects of low dielectric breakdown field strength, low energy storage density and high dielectric loss of most ceramic dielectric materials. In addition, the material has high density, excellent temperature stability and frequency stability of energy storage density and energy storage efficiency, can meet the requirements of different applications, is environment-friendly, and is expected to be used as a new generation of environment-friendly energy storage ceramic dielectric material.
Furthermore, the material of the invention obtains a slender hysteresis loop with a small loop area at room temperature (25 ℃), obtains excellent energy storage density and efficiency, and the energy storage density reaches 2.55-3.13J/cm3The energy storage efficiency reaches 82.25% -91.13%; in addition, the lead-free ceramic material with high energy storage and charge-discharge performance in the embodiment 3 has good energy storage density, high efficiency temperature stability and good frequency stability, and the energy storage density of the lead-free ceramic material under the electric field intensity of 200kV/cm is kept at 2.01-2.27J/cm at 10Hz and 20-140 DEG C3The energy storage efficiency is kept between 82.12% and 93.10%; the energy storage density of the material is kept at 2.14-2.28J/cm under the electric field intensity of 200kV/cm at room temperature and 1-100 Hz3The energy storage efficiency is kept between 87.93-92.18%, and in addition, when x is 0.3, the current density of the lead-free ceramic material with high energy storage and charge-discharge performance can reach 687.37A/cm at room temperature and 120kV/cm electric field intensity2The power density can reach 41.24MW/cm3The discharge time is as short as 125.6 ns. The energy storage density of the lead-free ceramic material with high energy storage and charge-discharge performance has good stability within the temperature range of 20-140 ℃ and the frequency range of 1-100 Hz, and the lead-free ceramic material is suitable for wider working temperature and frequency rangeAnd the field of application; and the lithium ion battery has excellent ultrahigh current density and power density and extremely high discharge speed, and is expected to be applied to the field of advanced energy storage.
The raw material powder is uniformly mixed, dried, sieved, pressed, molded and sintered to obtain the lead-free ceramic material with high energy storage and charge-discharge performance. The preparation process is simple and easy to realize, the used raw materials do not contain polluting elements such as lead and the like, the environment is not polluted, the used raw materials do not contain rare earth elements and noble metal elements, the raw materials are low in price, and the preparation method is suitable for industrial batch production.
Drawings
FIG. 1: XRD pattern of the lead-free ceramic material with high energy storage and charge-discharge performance prepared in example 1;
FIG. 2: XRD pattern of the lead-free ceramic material with high energy storage and charge-discharge performance prepared in example 2;
FIG. 3: the XRD pattern of the lead-free ceramic material with high energy storage and charge-discharge performance prepared in example 3;
FIG. 4: XRD pattern of the lead-free ceramic material with high energy storage and charge-discharge performance prepared in example 4;
FIG. 5: SEM image of the lead-free ceramic material with high energy storage and charge-discharge performance prepared in example 1;
FIG. 6: SEM image of the lead-free ceramic material with high energy storage and charge-discharge performance prepared in example 2;
FIG. 7: SEM image of the lead-free ceramic material with high energy storage and charge-discharge performance prepared in example 3;
FIG. 8: SEM image of the lead-free ceramic material with high energy storage and charge-discharge performance prepared in example 4;
FIG. 9: the hysteresis loop diagram (test frequency is 10Hz) of the lead-free ceramic material with high energy storage and charge-discharge performance prepared in the example 1 at room temperature;
FIG. 10: the lead-free ceramic material with high energy storage and charge-discharge performance prepared in example 2 has an electrical hysteresis loop diagram (the test frequency is 10Hz) at room temperature;
FIG. 11: the hysteresis loop diagram (test frequency is 10Hz) of the lead-free ceramic material with high energy storage and charge-discharge performance prepared in the example 3 at room temperature;
FIG. 12: the hysteresis loop diagram (test frequency is 10Hz) of the lead-free ceramic material with high energy storage and charge-discharge performance prepared in the example 4 at room temperature;
FIG. 13: the lead-free ceramic material with high energy storage and charge-discharge performance prepared in example 3 has hysteresis curves (test frequency is 10Hz) at 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 140 ℃ under the electric field intensity of 200 kV/cm;
FIG. 14: the lead-free ceramic material with high energy storage and charge-discharge performance prepared in example 3 has hysteresis curves at 1Hz, 5Hz, 10Hz, 50Hz, 100Hz and 200Hz (the test temperature is room temperature) at an electric field strength of 200 kV/cm;
FIG. 15: the lead-free ceramic material with high energy storage and charge-discharge performance prepared in the embodiment 3 has an underdamped discharge curve chart at room temperature and at the electric field intensity of 120 kV/cm;
FIG. 16: the lead-free ceramic material with high energy storage and charge-discharge performance prepared in the embodiment 3 has an over-damping discharge curve chart at room temperature and at the electric field intensity of 120 kV/cm;
FIG. 17: the change curve of the discharge energy density of the lead-free ceramic material with high energy storage and charge-discharge performance in room temperature and 120kV/cm electric field strength along with time is shown in example 3;
FIG. 18: the lead-free ceramic material with high energy storage and charge-discharge performance prepared in the embodiment 1 has a dielectric temperature spectrum under different test frequencies;
FIG. 19: the lead-free ceramic material with high energy storage and charge-discharge performance prepared in the embodiment 2 has a dielectric temperature spectrum under different test frequencies;
FIG. 20: the lead-free ceramic material with high energy storage and charge-discharge performance prepared in the embodiment 3 has a dielectric temperature spectrum under different test frequencies;
FIG. 21: the dielectric temperature spectrum of the lead-free ceramic material with high energy storage and charge-discharge performance prepared in the embodiment 4 under different test frequencies.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
A lead-free ceramic material with high energy storage and charge-discharge performance has a chemical formula as follows: (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3Wherein x represents a mole fraction, and x is 0.10. ltoreq. x.ltoreq.0.40.
The lead-free ceramic material with high energy storage and charge-discharge performance has the energy storage density of 2.55-3.13J/cm under the conditions of room temperature and 10Hz frequency3The energy storage efficiency is between 82.25 and 91.13 percent; the energy storage density of the lead-free ceramic material with high energy storage and charge-discharge performance in the embodiment 3 is kept at 2.01-2.27J/cm under the electric field intensity of 200kV/cm at the temperature of 20-140 ℃ at 10Hz3The energy storage efficiency is kept between 82.12% and 93.10%; under room temperature and 1-200 Hz, the lead-free ceramic material with high energy storage and charge-discharge performance in the embodiment 3 keeps the energy storage density at 2.14-2.28J/cm under the electric field intensity of 200kV/cm3And the energy storage efficiency is kept between 87.93% and 92.18%. In addition, the lead-free ceramic material with high energy storage and charge-discharge performance in the embodiment 3 has the current density of 687.37A/cm at room temperature and the electric field intensity of 120kV/cm2The power density can reach 41.24MW/cm3The discharge time is as short as 125.6 ns.
The preparation method of the lead-free ceramic material with high energy storage and charge-discharge performance comprises the following steps:
(1) according to formula (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3Analytically pure SrCO3、Na2CO3、TiO2、ZrO2And Bi2O3Preparing materials, wherein x represents a mole fraction, is more than or equal to 0.10 and less than or equal to 0.40, taking absolute ethyl alcohol as a medium, uniformly mixing by ball milling for 20-25 hours, then drying at 100 ℃, sieving by a 120-mesh sieve, briquetting, presintering for 2-6 hours at 850-950 ℃ to obtain blocky solids, crushing the blocky solids, and sieving by the 120-mesh sieve to obtain presintering powder;
(2) ball-milling the pre-sintered powder obtained in the step (1) for 20-25 hours by using absolute ethyl alcohol as a medium, then drying at 100 ℃, and sieving by using a 120-mesh sieve to obtain raw material powder;
(3) performing cold isostatic pressing on the raw material powder obtained in the step (2), wherein the pressure of the cold isostatic pressing is 190-210 MPa, and the pressure maintaining time is 3-5 minutes; pressing into a wafer under pressure, and then sintering into ceramic at 1200-1280 ℃ for 2-5 hours under heat preservation to obtain the lead-free ceramic material with high energy storage and charge-discharge performance;
(4) carrying out X-ray diffraction test on the prepared lead-free ceramic material with high energy storage and charge-discharge performance;
(5) carrying out SEM surface micro-morphology test on the prepared lead-free ceramic material with high energy storage and charge-discharge performance;
(6) processing the sintered sample into thin sheets with two smooth surfaces and a thickness of about 0.2mm, plating gold electrodes, testing the ferroelectric property of the samples at different temperatures and frequencies, calculating the energy storage characteristic and the energy storage density (W)1) Energy loss density (W)2) And the energy storage efficiency (η) is calculated as:
Figure BDA0002285631140000062
wherein W1And W2Respectively representing the energy storage density and energy loss density, PmaxDenotes the maximum polarization, PrIndicates remanent polarization, E indicates electric field intensity, P indicates polarization, and η indicates energy storage efficiency.
(7) Processing the sintered sample into a sheet with two smooth surfaces and a thickness of about 0.3mm, plating a silver electrode, testing the charge and discharge performance at room temperature and 120kV/cm electric field intensity, calculating the discharge characteristic, and calculating the current density (C)D) Power density (P)D) And discharge energy density (W)d) The calculation formula of (2) is as follows:
CD＝Imax/S (4)
PD＝ImaxE/2S (5)
Wd＝R∫I(t)2dt/V (6)
wherein C isDAnd PDRespectively representing current density and power density, ImaxDenotes the maximum current, WdRepresents the discharge energy density, E represents the electric field intensity, S represents the electrode area, R represents the load resistance, and V represents the sample volume.
The ball milling time in the step (1) and the step (2) is 20-25 hours.
The contents of the present invention will be further clarified by the following examples, which are not intended to limit the present invention.
Example 1:
the chemical formula of the ceramic material is as follows: (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3Wherein x represents a mole fraction, and x is 0.10.
The preparation method of the lead-free ceramic material with high energy storage and charge-discharge performance comprises the following steps:
(1) according to formula (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3Analytically pure SrCO3、Na2CO3、TiO2、ZrO2And Bi2O3Preparing materials, wherein x represents the mole fraction and is 0.10, using absolute ethyl alcohol as a medium, performing ball milling for 20 hours, uniformly mixing, drying at 100 ℃, sieving with a 120-mesh sieve, briquetting, presintering at 850 ℃ for 2 hours to obtain blocky solids, crushing the blocky solids, and sieving with the 120-mesh sieve to obtain presintering powder;
(2) ball-milling the pre-sintered powder obtained in the step (1) for 20 hours by using absolute ethyl alcohol as a medium, then drying at 100 ℃, and sieving by using a 120-mesh sieve to obtain raw material powder;
(3) performing cold isostatic pressing on the raw material powder obtained in the step (2), wherein the pressure of the cold isostatic pressing is 190MPa, and the pressure maintaining time is 3 minutes; pressing into a wafer under pressure, and then preserving heat at 1220 ℃ for 2 hours to sinter into ceramic to obtain the lead-free ceramic material with high energy storage and charge-discharge performance;
(4) the prepared lead-free ceramic material with high energy storage and charge-discharge performance is subjected to an X-ray diffraction test, as shown in figure 1, the XRD spectrum shows that the ceramic material obtained in the embodiment has a pure perovskite structure, does not contain other second phases and has high crystallinity; fig. 5 is an SEM image of the dielectric ceramic material prepared in this example, which shows that the ceramic material has a dense structure and no obvious defects such as pores, and table 5 shows that the average grain size of the dielectric ceramic material prepared in this example is 2.71 μm.
(5) Processing the sintered sample into a sheet with two smooth surfaces and a thickness of about 0.2mm, plating a gold electrode, and then testing the ferroelectric property at room temperature and a frequency of 10Hz, as shown in FIG. 9, the hysteresis loop of the ceramic material of the present embodiment is measured at room temperature, and the energy storage characteristic of the energy storage ceramic of the present embodiment can be calculated from the hysteresis loop, and the energy storage density of the energy storage ceramic of the present embodiment at room temperature can reach 2.55J/cm3The energy storage density can reach 82.25%. The energy storage characteristics of the lead-free energy storage ceramic material of the embodiment at room temperature are shown in table 1. The dielectric temperature spectra of the energy storage ceramic material at different test frequencies are shown in fig. 18, the dielectric constant of the energy storage ceramic material is increased firstly and then reduced within the temperature range of-150-250 ℃, and the corresponding dielectric loss is less than 0.15 at 5 different frequencies.
Example 2:
the chemical formula of the ceramic material is as follows: (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3Wherein x represents a mole fraction, and x is 0.20.
The preparation method of the lead-free ceramic material with high energy storage and charge-discharge performance comprises the following steps:
1) according to formula (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3Analytically pure SrCO3、Na2CO3、TiO2、ZrO2And Bi2O3Preparing materials, wherein x represents the mole fraction and is 0.20, taking absolute ethyl alcohol as a medium, performing ball milling for 24 hours, uniformly mixing, drying at 100 ℃, sieving with a 120-mesh sieve, briquetting, presintering at 900 ℃ for 4 hours to obtain blocky solids, crushing the blocky solids, and sieving with the 120-mesh sieve to obtain presintering powder;
(2) ball-milling the pre-sintered powder obtained in the step (1) for 24 hours by using absolute ethyl alcohol as a medium, then drying at 100 ℃, and sieving by using a 120-mesh sieve to obtain raw material powder;
(3) performing cold isostatic pressing on the raw material powder obtained in the step (2), wherein the pressure of the cold isostatic pressing is 200MPa, and the pressure maintaining time is 3 minutes; pressing into wafers under pressure, and then keeping the temperature at 1230 ℃ for 4 hours to sinter into ceramic to obtain the lead-free ceramic material with high energy storage and charge-discharge performance;
(4) the prepared lead-free ceramic material with high energy storage and charge-discharge performance is subjected to an X-ray diffraction test, as shown in figure 2, the XRD spectrum shows that the ceramic material obtained in the embodiment has a pure perovskite structure, does not contain other second phases and has high crystallinity; FIG. 6 is an SEM image of the dielectric ceramic material obtained in this example, which shows that the ceramic material has a dense structure and no obvious defects such as pores, and Table 5 shows that the average grain size of the dielectric ceramic material obtained in this example is 1.91 μm.
(5) Processing the sintered sample into a sheet with two smooth surfaces and a thickness of about 0.2mm, plating a gold electrode, and then testing the ferroelectric property at room temperature and a frequency of 10Hz, as shown in FIG. 10, the hysteresis loop of the ceramic material of the present embodiment is measured at room temperature, and the energy storage characteristic of the energy storage ceramic of the present embodiment can be calculated from the hysteresis loop, and the energy storage density of the energy storage ceramic of the present embodiment at room temperature can reach 2.85J/cm3And the energy storage density can reach 83.28 percent. The energy storage characteristics of the lead-free energy storage ceramic material of the embodiment at room temperature are shown in table 1. The dielectric temperature maps of the energy storage ceramic material at different test frequencies are shown in fig. 19, the dielectric constant of the energy storage ceramic material is increased firstly and then reduced within the temperature range of-150-250 ℃, and the corresponding dielectric loss is less than 0.15 at 5 different frequencies.
Example 3:
the chemical formula of the ceramic material is as follows: (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3Wherein x represents a mole fraction, and x is 0.30.
The preparation method of the lead-free ceramic material with high energy storage and charge-discharge performance comprises the following steps:
1) according to formula (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3Analytically pure SrCO3、Na2CO3、TiO2、ZrO2And Bi2O3Preparing materials, wherein x represents the mole fraction and is 0.30, taking absolute ethyl alcohol as a medium, performing ball milling for 24 hours, uniformly mixing, drying at 100 ℃, sieving with a 120-mesh sieve, briquetting, presintering at 950 ℃ for 4 hours to obtain blocky solids, crushing the blocky solids, and sieving with the 120-mesh sieve to obtain presintering powder;
(2) ball-milling the pre-sintered powder obtained in the step (1) for 24 hours by using absolute ethyl alcohol as a medium, then drying at 100 ℃, and sieving by using a 120-mesh sieve to obtain raw material powder;
(3) performing cold isostatic pressing on the raw material powder obtained in the step (2), wherein the pressure of the cold isostatic pressing is 200MPa, and the pressure maintaining time is 3 minutes; pressing into a wafer under pressure, and then preserving heat at 1270 ℃ for 4 hours to sinter into ceramic to obtain the lead-free ceramic material with high energy storage and charge-discharge performance;
(4) the prepared lead-free ceramic material with high energy storage and charge-discharge performance is subjected to an X-ray diffraction test, as shown in figure 3, an XRD (X-ray diffraction) spectrum shows that the ceramic material obtained in the embodiment has a pure perovskite structure, does not contain other second phases and has high crystallinity; fig. 7 is an SEM image of the dielectric ceramic material obtained in this example, which shows that the ceramic material has a dense structure and no obvious defects such as pores, and table 5 shows that the average grain size of the dielectric ceramic material obtained in this example is 1.68 μm.
(5) Processing the sintered sample into a thin sheet with two smooth surfaces and a thickness of about 0.2mm, plating gold on the electrode, and then performing 10H at room temperatureThe ferroelectric property of the energy-storage ceramic is measured under the z frequency, as shown in fig. 11, which is a hysteresis loop diagram of the ceramic material of the embodiment measured under the conditions of room temperature and 10Hz frequency, and the energy storage density of the energy-storage ceramic of the embodiment at room temperature can reach 3.13J/cm by calculating the energy storage characteristic from the hysteresis loop3The energy storage density can reach 91.13%. FIG. 13 is a graph showing hysteresis curves of the energy storage ceramic material at 20 deg.C, 40 deg.C, 60 deg.C, 80 deg.C, 100 deg.C, 120 deg.C and 140 deg.C under the conditions of 10Hz frequency and 200kV/cm electric field intensity, and energy storage characteristics are calculated from the hysteresis curves, wherein the energy storage density of the energy storage ceramic material is maintained at 2.01-2.27J/cm at 10Hz frequency and 20-140 deg.C3Meanwhile, the energy storage efficiency is kept between 82.12% and 93.10%, and the change rate of the energy storage efficiency is less than 12%. FIG. 14 is a hysteresis curve diagram of the energy-storing ceramic material of this embodiment at frequencies of 1Hz, 5Hz, 10Hz, 50Hz, 100Hz, and 200Hz under the conditions of room temperature and 200kV/cm electric field intensity, respectively, and the energy-storing characteristic is calculated from the hysteresis curve, and the energy-storing density of the energy-storing ceramic material of this embodiment is maintained at 2.14-2.28J/cm under the conditions of room temperature and 200kV/cm electric field intensity3In the meantime, the energy storage efficiency is kept between 87.93% and 92.18%, and the change rates are less than 6%, which shows that the energy storage ceramic material of the embodiment has high energy storage performance and shows good temperature stability and frequency stability. The energy storage characteristics of the lead-free energy storage ceramic material of the embodiment at room temperature are shown in table 1. Table 2 shows the energy storage characteristics of the energy storage ceramic material of this example at 25 deg.C, 40 deg.C, 55 deg.C, 70 deg.C, 85 deg.C, and 100 deg.C, respectively, at a frequency of 10Hz and at an electric field strength of 180 kV/cm. Table 3 shows the energy storage characteristics of the energy storage ceramic material of this example at 1Hz, 5Hz, 10Hz, 50Hz, 100Hz and 200Hz frequencies at room temperature and at an electric field strength of 200kV/cm, respectively. The dielectric temperature spectra of the energy storage ceramic material at different test frequencies are shown in fig. 20, the dielectric constant of the energy storage ceramic material tends to increase first and then decrease within the temperature range of-150 to 250 ℃, and the corresponding dielectric loss is less than 0.15 at 5 different frequencies.
(6) Processing the sintered sample into a sheet with two smooth surfaces and a thickness of about 0.3mm, plating a silver electrode, and then carrying out electric field intensity of 120kV/cm at room temperatureThe charge and discharge performance of the energy-storage ceramic is tested at room temperature, as shown in FIG. 15, the under-damped discharge curve of the ceramic material of the embodiment is measured at room temperature and 120kV/cm electric field intensity, and the charge and discharge characteristics are calculated through under-damped discharge, so that the current density of the energy-storage ceramic of the embodiment at room temperature and 120kV/cm electric field intensity can reach 687.37A/cm2The power density can reach 41.24
MW/cm3. FIG. 16 shows the over-damped discharge curve of the ceramic material of this embodiment measured at room temperature and 120kV/cm electric field strength, FIG. 17 shows the discharge energy density variation curve over time calculated from the over-damped discharge curve of the ceramic material of this embodiment measured at room temperature and 120kV/cm electric field strength, and the charge-discharge characteristics are calculated, so that the discharge energy density of the energy-storage ceramic of this embodiment at room temperature and 120kV/cm electric field strength can reach 1.17J/cm3The discharge time is as short as 125.6 ns. Table 4 shows the charge and discharge characteristics of the lead-free ceramic material with high energy storage and charge and discharge performance of example 3 at room temperature and at an electric field strength of 120 kV/cm.
Example 4:
the chemical formula of the ceramic material is as follows: (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3Wherein x represents a mole fraction, and x is 0.40.
The preparation method of the lead-free ceramic material with high energy storage and charge-discharge performance comprises the following steps:
(1) according to formula (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3Analytically pure SrCO3、Na2CO3、TiO2、ZrO2And Bi2O3Preparing materials, wherein x represents the mole fraction and is 0.40, ball-milling absolute ethyl alcohol serving as a medium for 25 hours, uniformly mixing, drying at 100 ℃, sieving with a 120-mesh sieve, briquetting, presintering at 950 ℃ for 6 hours to obtain blocky solids, crushing the blocky solids, and sieving with the 120-mesh sieve to obtain presintering powder;
(2) ball-milling the pre-sintered powder obtained in the step (1) for 25 hours by using absolute ethyl alcohol as a medium, then drying at 100 ℃, and sieving by using a 120-mesh sieve to obtain raw material powder;
(3) performing cold isostatic pressing on the raw material powder obtained in the step (2), wherein the pressure of the cold isostatic pressing is 210MPa, and the pressure maintaining time is 5 minutes; pressing into a wafer under pressure, and then preserving heat at 1280 ℃ for 6 hours to sinter into ceramic to obtain the lead-free ceramic material with high energy storage and charge-discharge performance;
(4) the prepared lead-free ceramic material with high energy storage and charge-discharge performance is subjected to an X-ray diffraction test, as shown in figure 4, the XRD spectrum shows that the ceramic material obtained in the embodiment has a pure perovskite structure, does not contain other second phases and has high crystallinity; FIG. 8 is an SEM image of the dielectric ceramic material obtained in this example, which shows that the ceramic material has a compact structure and no obvious defects such as pores, and Table 5 shows the average grain size of the dielectric ceramic material obtained in this example, which is 1.48 μm;
(5) processing the sintered sample into a sheet with two smooth surfaces and a thickness of about 0.2mm, plating a gold electrode, and then testing the ferroelectric property at room temperature under the frequency of 10Hz, as shown in FIG. 12, a hysteresis loop diagram of the ceramic material of the embodiment measured under the conditions of room temperature and 10Hz frequency is shown, and the energy storage property of the energy storage ceramic of the embodiment can be obtained by calculating the energy storage property from the hysteresis loop, wherein the energy storage density of the energy storage ceramic of the embodiment at room temperature can reach 3.08J/cm3The energy storage density can reach 87.80 percent. The energy storage characteristics of the lead-free energy storage ceramic material of the embodiment at room temperature are shown in table 1. The dielectric temperature spectra of the energy storage ceramic material at different test frequencies are shown in fig. 21, the dielectric constant of the energy storage ceramic material tends to increase first and then decrease within a temperature range of-150-250 ℃, and the corresponding dielectric loss is less than 0.15 at four different frequencies.
TABLE 1 examples lead-free high energy storage and Charge/discharge Performance ceramic materials with energy storage characteristics at room temperature and 10Hz
Table 2 example 3 energy storage characteristics of lead-free high energy storage and charging and discharging performance ceramic material at 10Hz frequency and different temperatures
Figure BDA0002285631140000132
Table 3 example 3 energy storage characteristics of lead-free high energy storage and charge and discharge performance ceramic material at room temperature at different frequencies
Figure BDA0002285631140000141
TABLE 4 EXAMPLE 3 Charge and discharge characteristics of lead-free high energy storage and Charge and discharge Performance ceramic materials at room temperature and 120kV/cm electric field strength
Figure BDA0002285631140000142
TABLE 5 average grain size after sintering of lead-free high energy storage and charging and discharging ceramic materials of the examples
As can be seen from Table 1, with Sr (Ti)0.85Zr0.15)O3The solid solution amount is continuously increased, the residual polarization strength of the energy storage ceramic material is increased after being reduced, the breakdown field strength shows the continuous increasing trend, higher energy storage density and energy storage efficiency can be obtained under a certain proportion, and the energy storage density and the energy storage efficiency can respectively reach 3.13J/cm at room temperature3And 91.13%; as shown in Table 2, the energy storage density of the energy storage ceramic material in example 3 of the invention can be maintained at 2.01-2.27J/cm at a temperature of 20-140 ℃ under the conditions that the frequency is 10Hz and the electric field strength is 200kV/cm3The energy storage efficiency is not greatly reduced along with the rise of the temperature, and the better temperature stability is shown; as can be seen from Table 3, the energy storage density at a frequency of 1 to 200Hz can be maintained at 2.14 to 2.28J/cm at room temperature and at an electric field strength of 200kV/cm3The energy storage efficiency can be kept between 87.93 and 92.18 percent, and the energy storage density and the efficiency do not fluctuate greatly and showBetter frequency stability. As can be seen from Table 4, the lead-free ceramic material with high energy storage and charge-discharge performance in example 3 has a current density of 687.37A/cm at room temperature and an electric field strength of 120kV/cm2The power density can reach 41.24MW/cm3The discharge time is as short as 125.6 ns. As can be seen from Table 5, with Sr (Ti)0.85Zr0.15)O3The increasing amount of solid solution and the decreasing average grain size of the energy storage ceramic material of the present invention are the main reasons for the increased dielectric breakdown field strength. It can be found from the above examples that Sr (Ti) is controlled0.85Zr0.15)O3The solid solution amount effectively overcomes the defects of low dielectric breakdown field strength, low energy storage density and high dielectric loss of most ceramic dielectric materials, and the prepared energy storage ceramic dielectric material has excellent temperature and frequency stability, is suitable for wider working temperature, frequency range and application field, has high power density and ultra-fast discharge rate, and is expected to be applied to an advanced energy storage system.
The contents of the present invention will be further clearly understood from the examples given above, but are not intended to limit the present invention.

Claims (9)

1. The lead-free ceramic material with high energy storage and charge-discharge performance is characterized by having the chemical formula as follows: (1-x) (Na)0.5Bi0.5)0.7Sr0.3TiO3-xSr(Ti0.85Zr0.15)O3Wherein x is more than or equal to 0.10 and less than or equal to 0.40.
2. The lead-free ceramic material with high energy storage and charge and discharge performance as claimed in claim 1, wherein the energy storage density of the lead-free ceramic material with high energy storage and charge and discharge performance is 2.55-3.13J/cm at room temperature and 10Hz frequency3The energy storage efficiency is 82.25% -91.13%; when x is 0.3, the current density is 687.37A/cm under the conditions of room temperature and 120kV/cm electric field intensity2The power density is 41.24MW/cm3The discharge time was 125.6 ns.
3. A method for preparing a lead-free ceramic material with high energy storage and charge-discharge properties according to claim 1 or 2, comprising the steps of:
(1) mixing SrCO3、Na2CO3、TiO2、ZrO2And Bi2O3Uniformly mixing to obtain raw material powder, briquetting, presintering to obtain blocky solid, and crushing and sieving the blocky solid to obtain presintering powder;
(2) ball-milling the pre-sintered powder obtained in the step (1) to obtain raw material powder;
(3) and (3) tabletting and molding the raw material powder obtained in the step (2), and sintering to obtain the ceramic material with lead-free high energy storage and charge and discharge performance.
4. The method for preparing the lead-free ceramic material with high energy storage and charge-discharge performance according to claim 3, wherein in the step (1), the mixing is uniform; and (3) ball milling is carried out by taking absolute ethyl alcohol as a medium, the ball milling time is 20-25 hours, and drying and sieving are carried out after ball milling.
5. The method for preparing the lead-free ceramic material with high energy storage and charge and discharge performance as claimed in claim 3, wherein in the step (1), the pre-sintering is performed at 850-950 ℃ for 2-6 hours.
6. The preparation method of the lead-free ceramic material with high energy storage and charge-discharge performance as claimed in claim 3, wherein in the step (2), the medium adopted by ball milling is absolute ethyl alcohol, the ball milling time is 20-25 hours, and drying is performed after ball milling.
7. The method for preparing a lead-free ceramic material with high energy storage and charge-discharge performance as claimed in claim 3, wherein in the step (3), the tabletting is performed by cold isostatic pressing.
8. The method for preparing a lead-free ceramic material with high energy storage and charge and discharge properties according to claim 3, wherein the cold isostatic pressing is performed under a pressure of 190 to 210MPa for 3 to 5 minutes.
9. The preparation method of the lead-free ceramic material with high energy storage and charge and discharge performance as claimed in claim 3, wherein in the step (3), the sintered ceramic is specifically kept at 1200-1280 ℃ for 2-5 hours.
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