CN112919907B - Lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage capacity and preparation method thereof - Google Patents

Lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage capacity and preparation method thereof Download PDF

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CN112919907B
CN112919907B CN202110181382.2A CN202110181382A CN112919907B CN 112919907 B CN112919907 B CN 112919907B CN 202110181382 A CN202110181382 A CN 202110181382A CN 112919907 B CN112919907 B CN 112919907B
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白王峰
刘继康
元勇军
吴诗婷
裴浪
鲍亮
张怀伟
陈逸凡
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Hangzhou Dianzi University
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Abstract

The invention relates to the functionThe field of materials and devices, aiming at the problem that the breakdown field strength and the effective energy storage density of the existing energy storage ceramic material are lower, discloses a lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage and a preparation method thereof, wherein the chemical composition of the ceramic is (1-x) NaNbO 3 ‑xCaTiO 3 Wherein x is more than or equal to 0.15 and less than or equal to 0.9. Preferably, x =0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9. Firstly, the CaTiO with the perovskite structure 3 The lead-free energy storage ceramic material is introduced into the sodium niobate-based ceramic for doping modification, so that high breakdown field strength is achieved, high energy storage density and high efficiency are obtained, the research direction of doping modification is expanded, and the lead-free energy storage ceramic material with application prospect is prepared.

Description

Lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage capacity and preparation method thereof
Technical Field
The invention relates to the field of functional materials and devices, in particular to a lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage capacity and a preparation method thereof.
Background
In recent years, with the miniaturization and integration of electronic components, higher demands have been made on electronic materials. Compared with energy storage devices such as batteries and chemical capacitors, the dielectric capacitor has the advantages of high power density, high discharge speed, long service life and the like, and the bulk ceramic dielectric capacitor has higher temperature stability and total energy storage amount. The energy-saving device can be widely applied to high-power pulse weapons, electromagnetic emitters, energy storage and hybrid power vehicle inverter equipment.
The energy storage ceramic material which is commercially used at present is mainly concentrated on a lead base materialHowever, the problem becomes more and more serious with the environmental deterioration, so it is very important to develop a novel lead-free energy storage material with enhanced energy storage efficiency and high energy storage capacity. As a lead-free antiferroelectric material, NaNbO 3 Have attracted renewed attention in recent energy storage applications. However, the antiferroelectric P phase having Pbma space groups therein is unstable at room temperature and tends to irreversibly switch to the ferroelectric phase in response to a large external electric field. According to the report, some NaNbO 3 The base solid solutions show stable antiferroelectric orthogonal P phase at room temperature, but very large phase switching hysteresis is observed, and in addition, the breakdown field strength and the effective energy storage density of the base solid solutions are relatively low, so that the potential of energy storage application is limited, and the base solid solutions cannot substitute for lead-based ceramic materials.
The invention discloses a novel high-energy-storage high-efficiency sodium niobate-based ceramic material with a composition formula of (1-x) [0.9NaNbO ], and a preparation method thereof under the patent number CN202011080909.4 3 -0.1Bi(Mg 2/3 Ta 1/3 )O 3 ]-x(Bi 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 And x is a mole percentage, x is more than or equal to 0 and less than or equal to 0.40, the invention also discloses a preparation method of the sodium niobate-based ceramic material, which comprises the novel high-energy-storage and high-efficiency sodium niobate-based ceramic material and also comprises the following steps: preparing sodium niobate-based ceramic powder; putting the sodium niobate-based ceramic powder into a ball milling tank for predetermined treatment, and pressing a product into a blank body for pre-sintering; pouring the product into a ball milling tank for carrying out predetermined treatment again after the presintering is finished, and pressing the powder into a wafer by using a die; sintering the wafer in a muffle furnace according to sintering conditions to prepare the sodium niobate-based ceramic material, and introducing a strong ferroelectric Bi (Mg) 2/3 Ta 1/3 )O 3 And (Bi) 0.5 Na 0.5 ) 0.7 Sr 0.3 TiO 3 With NaNbO 3 The antiferroelectric forms a uniform solid solution to improve the maximum polarization strength and breakdown field strength of the ceramic material, thereby improving the energy storage density of the dielectric ceramic material. It has the disadvantages thatThe effective energy storage density needs to be improved.
Disclosure of Invention
The invention aims to overcome the problems of low breakdown field strength and low effective energy storage density of the existing energy storage ceramic material, provides a lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage and a preparation method thereof, and firstly leads CaTiO with a perovskite structure 3 The lead-free energy storage ceramic material is introduced into the sodium niobate-based ceramic for doping modification, so that high breakdown field strength is achieved, high energy storage density and high efficiency are obtained, the research direction of doping modification is expanded, and the lead-free energy storage ceramic material with application prospect is prepared.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lead-free ferroelectric ceramic material with high energy storage efficiency and high energy storage capacity is prepared from (1-x) NaNbO 3 -xCaTiO 3 Wherein x is more than or equal to 0.15 and less than or equal to 0.9.
Preferably, x is 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9.
Compared with the prior art, the material design action mechanism of the invention is as follows:
(1)NaNbO 3 the antiferroelectric material has high maximum polarization strength under a low electric field due to a ferroelectric phase induced by a room temperature field, so that an innate condition is provided for high energy storage, and meanwhile, the further energy storage characteristics of the antiferroelectric material are limited by large residual polarization strength and small pressure resistance strength;
(2)CaTiO 3 the linear dielectric material has extremely low dielectric loss, nearly invariable adjustable dielectric, proper dielectric constant and large dielectric breakdown strength, and CaTiO is introduced 3 More active dipoles and larger compressive strength can be provided in the ceramic matrix;
(3) introduction of CaTiO 3 To NaNbO 3 In the matrix, NaNbO is retained 3 High maximum polarization strength, combined with CaTiO 3 The dielectric property and the ultrahigh pressure resistance strength of the composite material can simultaneously realize the energy storage characteristics of high energy storage density and high efficiency by utilizing the synergistic coupling effect;
therefore, the invention obtains the novel lead-free energy storage ceramic material with high energy storage density and high efficiency.
The preparation method of the lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage comprises the following preparation steps:
(1) primary burdening: with Na 2 CO 3 Powder and Nb 2 O 5 Powder, CaCO 3 Powder of TiO 2 The powder is taken as a raw material and is prepared according to the general formula of NaNbO 3 And CaTiO 3 Respectively proportioning the stoichiometric Na, the stoichiometric Nb, the stoichiometric Ca and the stoichiometric Ti to obtain a mixture;
(2) primary ball milling: adding absolute ethyl alcohol with the same quantity as the mixture into the mixture, and continuously ball-milling to uniformly mix the powder to form slurry;
(3) drying: baking the slurry in a constant-temperature oven at 78-80 ℃, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: mixing NaNbO 3 And CaTiO 3 Placing the powder in a grinding tool to be pre-pressed into material blocks, and pre-burning the material blocks;
(5) secondary burdening: NaNbO prepared by one-step mixing 3 And CaTiO 3 According to the general formula (1-x) NaNbO 3 -xCaTiO 3 Carrying out stoichiometric proportioning;
(6) secondary ball milling: grinding and grinding the secondarily-proportioned powder in a mortar to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously performing ball milling to uniformly mix the powder to form slurry;
(7) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(8) sieving the obtained prefabricated powder, mixing polyvinyl alcohol solution and distilled water as adhesives into the powder for granulation and molding, tabletting to prepare a green blank, removing glue, sintering to obtain porcelain, thinning and polishing the obtained ceramic wafer, placing the ceramic wafer in a furnace for high-temperature treatment, and sputtering gold electrodes on the upper surface and the lower surface respectively to obtain the lead-free ferroelectric ceramic material with enhanced energy storage efficiency.
In all steps, it is heavyThe method comprises separately synthesizing NaNbO 3 And CaTiO 3 The powder material is prepared by firstly ball-milling raw materials for 12-24h to obtain raw materials with uniform size, then placing the mixed raw materials into a grinding tool to be pressed into large blocks, and placing the large blocks into a sealed crucible to be presintered and synthesized, wherein the functions and the beneficial effects are as follows: (1) the raw material size is uniform, abnormal enlargement of crystal grains in the final ceramic is prevented, and uniformity of performance is facilitated; (2) the synthesis of the pressed large blocks is beneficial to full reaction and the uniformity of powder particles, so that the small loss and the uniform and small crystal grains are ensured, and the high compressive strength is further ensured; (3) the ceramic is prepared by secondary ball milling and mixing uniformly after synthesis, so that the energy barrier is reduced, the further completion of the reaction is ensured, and the compressive strength of the ceramic is improved; because the loss is small, the crystal grain size is small and uniform, the compressive strength and the repeatability of the material are greatly improved, and the high energy storage characteristic is ensured.
Preferably, in the step (1), Na is used for preparing the material 2 CO 3 Powder and Nb 2 O 5 Powder, CaCO 3 Powder, TiO 2 The purity of the powder is more than 99%.
Preferably, in the step (2), in the first ball milling process: the ball milling time is 12-24 h; in the step (6), the grinding time is 30-40min, and the continuous ball milling time is 12-24 h.
Preferably, in the step (4), NaNbO is used 3 The presintering temperature is 800- 3 The presintering temperature is 1075-1125 ℃, and the heat preservation time is 2-4 h.
Preferably, in the step (8), the polyvinyl alcohol solution is added in an amount of 8 to 10% by mass based on the mass of the powder, and the distilled water is added in an amount of 2 to 5% by mass based on the mass of the powder.
Preferably, in the step (8), the glue discharging process comprises: discharging the glue at the temperature of 550-600 ℃ and calcining for 5-10 h.
Preferably, in the step (8), sintering and forming are carried out after glue discharging, the sintering temperature is 1125-.
Preferably, in the step (8), the high-temperature treatment process comprises: the temperature is 550 ℃ and 600 ℃, and the heat preservation time is 2-4 h.
Therefore, the invention has the following beneficial effects:
(1) the energy storage dielectric ceramic material provided by the invention realizes high-efficiency energy storage characteristic, greatly improves breakdown strength which exceeds 500kV/cm, and can release energy with density of 3.9-4.9J/cm 3 The efficiency is 83-96%;
(2) the energy-storage ceramic material is prepared by the traditional energy-storage ceramic process, has low preparation cost and simple process, is suitable for large-scale industrial production, obviously improves the energy storage performance of the doped and modified ceramic material, and promotes the research progress of the lead-free energy-storage material;
(3) the preparation method provided by the invention has great guiding significance for improving the compressive strength of the energy storage material, not only can effectively improve the compressive strength, but also can ensure the repeatability of the energy storage performance of the ceramic;
drawings
Fig. 1 is a scanning electron microscope photograph of a type of energy storage efficiency enhanced high energy storage lead-free ferroelectric ceramic prepared in example 1.
Fig. 2 is a ferroelectric hysteresis loop of a type of energy storage efficiency enhanced high energy storage lead-free ferroelectric ceramic prepared in example 1.
Fig. 3 shows the effective energy storage density and efficiency of the lead-free ferroelectric ceramic with enhanced energy storage efficiency obtained in example 1 as a function of the electric field.
Fig. 4 is a ferroelectric hysteresis loop of a type of lead-free ferroelectric ceramic with enhanced energy storage efficiency prepared in example 2.
Fig. 5 shows the effective energy storage density and efficiency of the lead-free ferroelectric ceramic with enhanced energy storage efficiency obtained in example 2 as a function of the electric field.
Fig. 6 is a ferroelectric hysteresis loop of a type of energy storage efficiency enhanced high energy storage lead-free ferroelectric ceramic prepared in example 3.
Fig. 7 shows the effective energy storage density and efficiency as a function of electric field for a class of energy storage efficiency enhanced high energy storage lead-free ferroelectric ceramics prepared in example 3.
Fig. 8 is a hysteresis loop of a type of energy storage efficiency enhanced high energy storage lead-free ferroelectric ceramic made in example 4.
Fig. 9 shows the effective energy storage density and efficiency as a function of electric field for a class of energy storage efficiency enhanced high energy storage lead-free ferroelectric ceramics prepared in example 4.
Fig. 10 is a hysteresis loop of the lead-free ferroelectric ceramic prepared in comparative example 1.
Fig. 11 is a hysteresis loop of the lead-free ferroelectric ceramic prepared in comparative example 2.
Fig. 12 is a hysteresis loop of the lead-free ferroelectric ceramic prepared in comparative example 3.
Detailed Description
The invention is further described with reference to specific embodiments.
General examples
A lead-free ferroelectric ceramic material with high energy storage efficiency and high energy storage capacity is prepared from (1-x) NaNbO 3 -xCaTiO 3 Wherein x is not less than 0.15 and not more than 0.9 (said x is 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9).
The preparation method of the lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage comprises the following preparation steps:
(1) primary burdening: with Na 2 CO 3 Powder and Nb 2 O 5 Powder, CaCO 3 Powder, TiO 2 The powder is taken as a raw material and is prepared according to the general formula of NaNbO 3 And CaTiO 3 Respectively proportioning the stoichiometric Na, the stoichiometric Nb, the stoichiometric Ca and the stoichiometric Ti to obtain a mixture; na (Na) 2 CO 3 Powder and Nb 2 O 5 Powder, CaCO 3 Powder, TiO 2 The purity of the powder is more than 99%.
(2) Primary ball milling: adding absolute ethyl alcohol with the same quantity as the mixture into the mixture, and continuously ball-milling for 12-24h to uniformly mix the powder to form slurry;
(3) drying: baking the slurry in a constant-temperature oven at 78-80 ℃, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: mixing NaNbO 3 And CaTiO 3 Putting the powder into a grinding tool to be pre-pressed into material blocks, and pre-burning the material blocks; NaNbO 3 The pre-sintering temperature is 800-The temperature is 2 to 4 hours, CaTiO 3 The presintering temperature is 1075-1125 ℃, and the heat preservation time is 2-4 h.
(5) Secondary burdening: NaNbO prepared by one-step mixing 3 And CaTiO 3 According to the general formula (1-x) NaNbO 3 -xCaTiO 3 Carrying out stoichiometric proportioning;
(6) secondary ball milling: grinding the secondary-blended powder in a mortar for 30-40min to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously performing ball milling for 12-24h to uniformly mix the powder to form slurry;
(7) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(8) sieving the obtained prefabricated powder, doping a polyvinyl alcohol solution and distilled water into the powder for granulation and molding, tabletting to prepare a green body, removing glue at the temperature of 550-600 ℃ for 5-10h, preserving heat at the temperature of 1125-1175 ℃ for 2-4h, sintering to obtain porcelain, thinning and polishing the obtained ceramic plate, placing the ceramic plate in a furnace for high-temperature treatment at the temperature of 550-600 ℃ for 2-4h, and sputtering gold electrodes on the upper surface and the lower surface respectively to obtain the lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage capacity; the mass of the mixed polyvinyl alcohol solution is the same as that of the powder, the mass concentration of the polyvinyl alcohol solution is 8-10%, and the mass of the mixed distilled water is 2-5% of that of the powder.
Example 1
A lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage has a chemical general formula: (1-x) NaNbO 3 -xCaTiO 3 ，x＝0.2。
The preparation method of the lead-free ferroelectric ceramic material with the enhanced energy storage efficiency and the high energy storage capacity comprises the following preparation steps:
(1) primary burdening: with Na 2 CO 3 Powder and Nb 2 O 5 Powder, CaCO 3 Powder, TiO 2 The powder is used as raw material (purity is more than 99%) according to the general formula of NaNbO 3 And CaTiO 3 Proportioning the stoichiometric amounts of Na, Nb, Ca and Ti;
(2) primary ball milling: and adding absolute ethyl alcohol into the mixture in an amount equal to the mixture, and continuously performing ball milling for 12 hours. The powder is uniformly mixed to form slurry, so that the comprehensive performance of the ceramic material can be further improved;
(3) and (3) drying: baking the slurry in a constant-temperature (80 ℃) oven, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: mixing NaNbO 3 And CaTiO 3 Placing the powder material in a grinding tool, prepressing the powder material into material blocks, preburning the material blocks, and using NaNbO 3 Presintering temperature is 800 ℃, heat preservation time is 4 hours, CaTiO 3 The presintering temperature is 1075 ℃, and the heat preservation time is 4 hours.
(5) Secondary burdening: NaNbO prepared by one-step mixing 3 And CaTiO 3 According to the general formula (1-x) NaNbO 3 -xCaTiO 3 Carrying out stoichiometric proportioning;
(6) secondary ball milling: grinding the secondary-burdened powder in a mortar for 40min to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously ball-milling for 24h to uniformly mix the powder to form slurry;
(7) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(8) sieving the obtained prefabricated powder, adding a polyvinyl alcohol solution and distilled water into the powder for granulation and molding, wherein the mass of the added polyvinyl alcohol solution is the same as that of the powder, the concentration of the polyvinyl alcohol solution (PVA) is 8%, and the mass of the added distilled water is 5% of that of the powder. Tabletting to obtain a green body, removing glue at 550 ℃, and calcining for 10 h. And after removing the glue, sintering and forming, wherein the sintering temperature is 1125 ℃, and the heat preservation time is 4 h. Sintering to form ceramic, thinning and polishing the obtained ceramic wafer, and placing the ceramic wafer in a furnace for high-temperature treatment at 550 ℃ for 4 hours. And respectively sputtering gold electrodes on the upper surface and the lower surface to obtain the lead-free ferroelectric ceramic material with the enhanced energy storage efficiency and high energy storage capacity.
FIG. 1 is a picture of the microstructure of a class of energy storage efficiency enhanced high energy storage lead-free ferroelectric ceramics of this example. As can be seen from the figure, the ceramic material exhibits a very dense structure, which contributes to the improved breakdown strength of the ceramic.
Fig. 2 is a unidirectional hysteresis loop of a type of energy storage efficiency enhanced high energy storage lead-free ferroelectric ceramic of this example measured at room temperature and 10 Hz. It can be seen that the hysteresis loop of the ceramic is relatively slender, and the electric field intensity can reach 370 kV/cm.
FIG. 3 shows the variation of the effective energy storage density and efficiency of the lead-free ferroelectric ceramic with enhanced energy storage efficiency and high energy storage according to the electric field of the example, wherein the effective energy storage density and efficiency are respectively 3.94J/cm at 370kV/cm 3 ，83.7％。
Example 2
A lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage has a chemical general formula: (1-x) NaNbO 3 -xCaTiO 3 ，x＝0.4。
The preparation method of the lead-free ferroelectric ceramic material with the enhanced energy storage efficiency and the high energy storage capacity comprises the following preparation steps:
(1) primary burdening: with Na 2 CO 3 Powder and Nb 2 O 5 Powder, CaCO 3 Powder, TiO 2 The powder is used as raw material (purity is more than 99%) according to the general formula of NaNbO 3 And CaTiO 3 Proportioning the stoichiometric amounts of Na, Nb, Ca and Ti;
(2) primary ball milling: and adding absolute ethyl alcohol into the mixture in an equal amount to the mixture, and continuously performing ball milling for 24 hours. The powder is uniformly mixed to form slurry, so that the comprehensive performance of the ceramic material can be further improved;
(3) drying: baking the slurry in a constant-temperature (78 ℃) oven, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: mixing NaNbO 3 And CaTiO 3 Placing the powder material in a grinding tool, prepressing the powder material into material blocks, preburning the material blocks, and using NaNbO 3 Presintering at 850 deg.C for 2 hr, and maintaining the temperature for 2 hr 3 The presintering temperature is 1125 ℃, and the heat preservation time is 2 h.
(5) Secondary burdening: NaNbO prepared by one-step mixing 3 And CaTiO 3 According to the general formula (1-x) NaNbO 3 -xCaTiO 3 Carrying out stoichiometric preparationFeeding;
(6) secondary ball milling: grinding and grinding the secondarily-proportioned powder in a mortar to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously performing ball milling for 12-24 hours to uniformly mix the powder to form slurry;
(7) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(8) sieving the obtained prefabricated powder, adding a polyvinyl alcohol solution and distilled water into the powder for granulation and molding, wherein the mass of the added polyvinyl alcohol solution is the same as that of the powder, the concentration of the polyvinyl alcohol solution (PVA) is 10%, and the mass of the added distilled water is 2% of that of the powder. Tabletting to obtain a green body, removing glue at 600 ℃, and calcining for 5 h. And after glue discharging, sintering and forming are carried out, wherein the sintering temperature is 1175 ℃, and the heat preservation time is 2 hours. Sintering to form ceramic, thinning and polishing the obtained ceramic wafer, and placing the ceramic wafer in a furnace for high-temperature treatment at the temperature of 600 ℃ and preserving heat for 2 hours. And respectively sputtering gold electrodes on the upper surface and the lower surface to obtain the lead-free ferroelectric ceramic material with the enhanced energy storage efficiency and high energy storage capacity.
Fig. 4 is a unidirectional hysteresis loop of a type of energy storage efficiency enhanced high energy storage lead-free ferroelectric ceramic of this example measured at room temperature and 10 Hz. It can be seen from the figure that the hysteresis loop of the ceramic is relatively slender, and the electric field intensity can reach as high as 500 kV/cm. .
FIG. 5 shows the variation of the effective energy storage density and efficiency of the lead-free ferroelectric ceramic with the electric field, which is enhanced by the energy storage efficiency of the example, at 500kV/cm, the effective energy storage density and efficiency are 4.7J/cm 3 ，91.5％。
Example 3
A lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage has a chemical general formula: (1-x) NaNbO 3 -xCaTiO 3 ，x＝0.6。
The preparation method of the lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage comprises the following preparation steps:
(1) primary burdening: with Na 2 CO 3 Powder and Nb 2 O 5 Powder, CaCO 3 Powder, TiO 2 The powder is used as raw material (purity is more than 99%) according to the general formula of NaNbO 3 And CaTiO 3 Proportioning the stoichiometric amounts of Na, Nb, Ca and Ti;
(2) primary ball milling: and adding absolute ethyl alcohol into the mixture in an equal amount to the mixture, and continuously performing ball milling for 15 hours. The powder is uniformly mixed to form slurry, so that the comprehensive performance of the ceramic material can be further improved;
(3) drying: baking the slurry in a constant-temperature (80 ℃) oven, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: mixing NaNbO 3 And CaTiO 3 Placing the powder material in a grinding tool, prepressing the powder material into material blocks, preburning the material blocks, and using NaNbO 3 Presintering temperature is 810 ℃, heat preservation time is 2.5h, and CaTiO 3 The pre-sintering temperature is 1115 ℃, and the heat preservation time is 3.5 h.
(5) Secondary burdening: NaNbO prepared by one-step mixing 3 And CaTiO 3 According to the general formula (1-x) NaNbO 3 -xCaTiO 3 Carrying out stoichiometric proportioning;
(6) secondary ball milling: grinding the secondary-burdened powder in a mortar for 38min to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously performing ball milling for 22h to uniformly mix the powder to form slurry;
(7) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(8) sieving the obtained prefabricated powder, adding a polyvinyl alcohol solution and distilled water into the powder for granulation and molding, wherein the mass of the added polyvinyl alcohol solution is the same as that of the powder, the concentration of the used polyvinyl alcohol solution (PVA) is 9.5%, and the mass of the added distilled water is 3% of that of the powder. Tabletting to obtain a green body, removing glue at 590 ℃, and calcining for 9 h. And sintering and forming are carried out after the glue is removed, the sintering temperature is 1160 ℃, and the heat preservation time is 3.5 hours. Sintering to form ceramic, thinning and polishing the obtained ceramic wafer, and placing the ceramic wafer in a furnace for high-temperature treatment at 590 ℃ for heat preservation for 3.5 hours. And respectively sputtering gold electrodes on the upper surface and the lower surface to obtain the lead-free ferroelectric ceramic material with the enhanced energy storage efficiency and high energy storage capacity.
Fig. 6 is a unidirectional hysteresis loop of a type of energy storage efficiency enhanced high energy storage lead-free ferroelectric ceramic of this example measured at room temperature and 10 Hz. It can be seen from the figure that the hysteresis loop of the ceramic is relatively slender, and the electric field intensity can reach 560 kV/cm. .
FIG. 7 shows the variation of effective energy storage density and efficiency with electric field of a class of energy storage efficiency enhanced high energy storage lead-free ferroelectric ceramic of this example, the effective energy storage density and efficiency are respectively 4.14J/cm at 560kV/cm 3 ，91.7％。
Example 4
A lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage has a chemical general formula: (1-x) NaNbO 3 -xCaTiO 3 ，x＝0.8。
The preparation method of the lead-free ferroelectric ceramic material with the enhanced energy storage efficiency and the high energy storage capacity comprises the following preparation steps:
(1) primary burdening: with Na 2 CO 3 Powder and Nb 2 O 5 Powder, CaCO 3 Powder, TiO 2 The powder is used as raw material (purity is more than 99%) according to the general formula of NaNbO 3 And CaTiO 3 Proportioning the stoichiometric amounts of Na, Nb, Ca and Ti;
(2) primary ball milling: and adding absolute ethyl alcohol with the same quantity as the mixture into the mixture, and continuously ball-milling for 22 hours. The powder is uniformly mixed to form slurry, so that the comprehensive performance of the ceramic material can be further improved;
(3) and (3) drying: baking the slurry in a constant-temperature (80 ℃) oven, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: mixing NaNbO 3 And CaTiO 3 Placing the powder material in a grinding tool, prepressing the powder material into material blocks, preburning the material blocks, and using NaNbO 3 Presintering temperature is 810 ℃, heat preservation time is 2.5h, CaTiO 3 The pre-sintering temperature is 1095 ℃, and the heat preservation time is 2.5 h.
(5) Secondary burdening: NaNbO prepared by one-step mixing 3 And CaTiO 3 According to the formula(1-x)NaNbO 3 -xCaTiO 3 Carrying out stoichiometric proportioning;
(6) secondary ball milling: grinding the secondary-burdened powder in a mortar for 32min to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously ball-milling for 14h to uniformly mix the powder to form slurry;
(7) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(8) sieving the obtained prefabricated powder, adding a polyvinyl alcohol solution and distilled water into the powder for granulation and molding, wherein the mass of the added polyvinyl alcohol solution is the same as that of the powder, the concentration of the used polyvinyl alcohol solution (PVA) is 8.5%, and the mass of the added distilled water is 2.5% of that of the powder. Tabletting to obtain a green body, discharging glue at 560 ℃, and calcining for 6 h. And (4) sintering and forming after removing the glue, wherein the sintering temperature is 1150 ℃, and the heat preservation time is 3 h. Sintering to form ceramic, thinning and polishing the obtained ceramic wafer, and placing the ceramic wafer in a furnace for high-temperature treatment at 570 ℃ for 2.5 hours. And respectively sputtering gold electrodes on the upper surface and the lower surface to obtain the lead-free ferroelectric ceramic material with the enhanced energy storage efficiency and high energy storage capacity.
Fig. 8 is a unidirectional hysteresis loop of a class of energy storage efficiency enhanced high energy storage lead-free ferroelectric ceramic of this example measured at room temperature and 10 Hz. It can be seen from the figure that the breakdown field strength of the ceramic is as high as 600 kV/cm.
FIG. 9 shows the variation of effective energy storage density and efficiency of the prepared lead-free ferroelectric ceramic with enhanced energy storage efficiency and high energy storage capacity with electric field, wherein the effective energy storage density and efficiency are respectively 4.9J/cm at 600kV/cm 3 ，96％。
Comparative example 1 (different from example 1 in that x is 0.05.)
NaNbO according to the formula (1-x) 3 -xCaTiO 3 And x is 0.05, the preparation was carried out as in example 1 above.
Comparative example 2 (different from example 1 in that x is 0.1.)
NaNbO according to the formula (1-x) 3 -xCaTiO 3 And x is 0.1, the preparation is carried out,the procedure was as in example 1 above.
Comparative example 3 (differing from example 3 in that example 3 uses NaNbO 3 And CaTiO 3 Separately synthesized, then ball-milled and mixed evenly for the second time, and the (1-x) NaNbO is synthesized by the one-step raw material adopted in the comparative example 2 3 -xCaTiO 3 ，x＝0.6)
NaNbO according to the formula (1-x) 3 -xCaTiO 3 And x is 0.6, the preparation is carried out, the preparation process is different in that the raw materials are subjected to ball milling once, and other preparation steps are consistent with the steps in the above example 3.
The relevant performance evaluation parameter indexes of the lead-free ferroelectric ceramic materials with enhanced energy storage efficiency prepared in examples 1-4 and comparative examples 1-3 are shown in table 1.
Table 1 shows the performance evaluation indexes of the items and the energy storage efficiency reinforced high-energy storage lead-free ferroelectric ceramic material
Item Compressive strength (kV/cm) Recoverable density (J/cm) 3 ) Efficiency (%)
Example 1 370 3.94 83.7
Example 2 500 4.7 91.5
Example 3 560 4.14 91.7
Example 4 600 4.9 96
Comparative example 1 300 0.28 5.6
Comparative example 2 340 2.18 70％
Comparative example 3 520 2.78 62.9
And (4) conclusion: it can be seen from examples 1 to 4 and comparative examples 1 to 3 that within the scope of the additive materials, additive amounts and preparation processes defined in the present invention, a superior energy storage efficiency reinforced high energy storage lead-free ferroelectric ceramic material can be obtained, and the prepared ferroelectric ceramic material has high energy storage density and high efficiency, and realizes a great increase in high-efficiency energy storage characteristics and breakdown strength.
The property obtained in comparative example 1 was a storage density of 0.28J/cm 3 The efficiency was 5.6%, the main reason for this being that it had a significant ferroelectric phase, CaTiO 3 Low content of materialHowever, the ferroelectric phase is the main phase, and the withstand voltage is not high.
The property obtained in comparative example 2 was a storage density of 2.18J/cm 3 The efficiency is 70%, the main reason for this being that it has a certain amount of ferroelectric phase, CaTiO 3 The content is relatively small, and the material still takes the ferroelectric phase as the main material.
The property obtained in comparative example 3 was a storage density of 2.78J/cm 3 The efficiency is 62.9 percent, and the main reasons are that the raw materials are synthesized at one time, the defects of the ceramic are more, the loss is large, the grain size is not uniform, the compression strength of the material is greatly limited, and the hysteresis of the material is increased.
From the data of examples 1-4 and comparative examples 1-3, it can be seen that the above requirements can be satisfied in all aspects only by the scheme within the scope of the claims of the present invention, and an optimized scheme can be obtained, and the lead-free ferroelectric ceramic material with enhanced energy storage efficiency and excellent energy storage efficiency and the preparation method thereof can be obtained. The change of the mixture ratio, the replacement/addition/subtraction of raw materials or the change of the feeding sequence can bring corresponding negative effects.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (7)

1. A process for preparing the lead-free ferroelectric ceramic with high energy-accumulating efficiency is characterized by that the chemical composition of said ceramic is (1-x) NaNbO 3 -xCaTiO 3 Wherein x is more than or equal to 0.15 and less than or equal to 0.9;
the preparation method comprises the following preparation steps:
(1) primary burdening: with Na 2 CO 3 Powder and Nb 2 O 5 Powder, CaCO 3 Powder, TiO 2 The powder is taken as a raw material and is prepared according to the general formula of NaNbO 3 And CaTiO 3 Respectively proportioning the stoichiometric Na, the stoichiometric Nb, the stoichiometric Ca and the stoichiometric Ti to obtain a mixture;
(2) primary ball milling: adding absolute ethyl alcohol with the same quantity as the mixture into the mixture, and continuously ball-milling to uniformly mix the powder to form slurry;
(3) drying: baking the slurry in a constant-temperature oven at 78-80 ℃, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(4) and (3) tabletting and pre-sintering: mixing NaNbO 3 And CaTiO 3 Putting the powder into a die to be pre-pressed into material blocks, and pre-burning the material blocks; NaNbO 3 The presintering temperature is 800- 3 The presintering temperature is 1075 and 1125 ℃, and the heat preservation time is 2-4 h;
(5) secondary burdening: NaNbO prepared by one-step mixing 3 And CaTiO 3 According to the general formula (1-x) NaNbO 3 -xCaTiO 3 Carrying out stoichiometric proportioning;
(6) secondary ball milling: grinding the powder prepared in the secondary preparation in a mortar to obtain primary powder, adding absolute ethyl alcohol with the same amount as the primary powder into the obtained primary powder, and continuously performing ball milling to uniformly mix the powder to form slurry;
(7) drying: placing the slurry in a constant-temperature oven for baking, removing absolute ethyl alcohol, and grinding the slurry into powder in a mortar;
(8) sieving the obtained prefabricated powder, mixing a polyvinyl alcohol solution and distilled water as adhesives into the powder for granulation and molding, tabletting to prepare a green blank, removing the adhesives, and sintering to obtain porcelain, wherein the sintering temperature is 1125-1175 ℃, and the heat preservation time is 2-4 h; and thinning and polishing the obtained ceramic wafer, placing the ceramic wafer in a furnace for high-temperature treatment, and sputtering gold electrodes on the upper surface and the lower surface respectively to obtain the lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage capacity.
2. The method of claim 1, wherein x =0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9.
3. The method according to claim 1, wherein in the step (1), Na is added as a material 2 CO 3 Powder and Nb 2 O 5 Powder, CaCO 3 Powder, TiO 2 The purity of the powder is more than 99%.
4. The method according to claim 1, wherein in the step (2), in one ball milling process: the ball milling time is 12-24 h; in the step (6), the grinding time is 30-40min, and the continuous ball milling time is 12-24 h.
5. The process according to claim 1, wherein in the step (8), the polyvinyl alcohol solution is added in an amount of 8 to 10% by mass based on the mass of the powder, and the distilled water is added in an amount of 2 to 5% by mass based on the mass of the powder.
6. The method according to claim 1, wherein in the step (8), the step of discharging the glue comprises: discharging the glue at the temperature of 550-600 ℃ and calcining for 5-10 h.
7. The method according to claim 1, wherein in the step (8), the high-temperature treatment process comprises: the temperature is 550 ℃ and 600 ℃, and the heat preservation time is 2-4 h.
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