CN113999004A - Lead-free high-energy-storage-density ceramic material and preparation method thereof - Google Patents

Lead-free high-energy-storage-density ceramic material and preparation method thereof Download PDF

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CN113999004A
CN113999004A CN202111315942.5A CN202111315942A CN113999004A CN 113999004 A CN113999004 A CN 113999004A CN 202111315942 A CN202111315942 A CN 202111315942A CN 113999004 A CN113999004 A CN 113999004A
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energy storage
powder
lead
ceramic material
high energy
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CN113999004B (en
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闫养希
覃文杰
李智敏
张东岩
张茂林
靳立
郝跃
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Xidian University
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Abstract

The invention relates to a lead-free high energy storage density ceramic material and a preparation method thereof, wherein the lead-free high energy storage density ceramic material has the chemical formula as follows: (1-x) [ (1-y) BaTiO3‑yBi(M′M″)O3]‑xBi0.5Na0.5TiO3Wherein x is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0.03 and less than or equal to 0.4, M 'is Zn, Mg, Li or Ni, and M' is Hf, Ta, Nb or Ti. The lead-free high energy storage density ceramic material is prepared by taking BNT with great saturation polarization strength as a third component and a relaxor ferroelectric BaTiO3‑Bi(M′M″)O3The BT-BM 'M' -BNT system is obtained through solid solution, and the lead-free ceramic material with high energy storage density of the invention still keeps extremely low residual polarization strength under the condition of obviously improving the saturation polarization strength and can obtain extremely high energy storage density under extremely low field intensity.

Description

Lead-free high-energy-storage-density ceramic material and preparation method thereof
Technical Field
The invention belongs to the field of dielectric energy storage ceramic materials, and particularly relates to a lead-free high-energy storage density ceramic material and a preparation method thereof.
Background
With the continuous development of new renewable energy storage and utilization and electronic information technology, energy storage medium materials play an increasingly important role in various electronic and power systems. The dielectric energy storage capacitor can generate a large amount of electric energy in a very short time due to high power density (ultra-fast charge-discharge rate), has very long cycle life and high safety, is widely applied to the fields of nuclear physics technology, medical operation laser, directional energy weapons and the like, and becomes one of key elements in a pulse power system. With the development of power electronic device systems toward miniaturization, light weight and integration, the existing energy storage dielectric capacitor can not meet the increasing demand of society, and the development of dielectric materials with high energy storage characteristics is strategically necessary.
The dielectric materials currently applied to the energy storage dielectric capacitor mainly comprise five major categories of polymers, ceramic-polymer composite materials, glass ceramics and ceramics. The dielectric ceramic has high comprehensive performance such as medium breakdown field strength, low dielectric loss, excellent temperature stability, fatigue resistance and the like, and can better meet the requirements of the fields such as aerospace, electromagnetic pulse weapons and the like on the energy storage dielectric capacitor. Dielectric ceramics can be generally classified into ferroelectric ceramics, antiferroelectric ceramics, linear dielectric ceramics, and relaxor ferroelectric ceramics. The relaxor ferroelectric has a gentle dielectric peak due to dispersion phase transition, namely, has good temperature stability; meanwhile, the relaxor ferroelectric material has a thin and long ferroelectric hysteresis loop like an antiferroelectric material, has lower energy loss while releasing more energy, and has the characteristics of higher energy storage density and energy storage efficiency.
However, most of the existing relaxor ferroelectric energy storage material systems have the problems of low maximum saturation polarization intensity and low energy storage density caused by medium dielectric breakdown field intensity, which seriously hinders the practical application field of the relaxor ferroelectric energy storage material systems.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a lead-free high-energy-storage-density ceramic material and a preparation method thereof. The technical problem to be solved by the invention is realized by the following technical scheme:
the invention provides a lead-free high energy storage density ceramic material, which has a chemical formula as follows: (1-x) [ (1-y) BaTiO3-yBi(M′M″)O3]-xBi0.5Na0.5TiO3Wherein x is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0.03 and less than or equal to 0.4, M 'is Zn, Mg, Li or Ni, and M' is Hf, Ta, Nb or Ti.
The invention provides a preparation method of a lead-free high-energy-storage-density ceramic material, which comprises the following steps:
step 1: according to (1-x) [ (1-y) BaTiO3-yBi(M′M″)O3]-xBi0.5Na0.5TiO3In the stoichiometric ratio, a Ba-containing compound, a Ti-containing compound, a Bi-containing compound, a Na-containing compound, an M 'containing compound and an M' containing compound are prepared to obtain a mixed material, wherein x is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0.03 and less than or equal to 0.4, M 'is Zn, Mg, Li or Ni, and M' is Hf, Ta, Nb or Ti;
step 2: sequentially carrying out ball milling, drying, grinding and sieving on the mixed material, and then carrying out first presintering treatment to obtain first presynthesized powder;
and step 3: sequentially carrying out ball milling, drying, grinding and sieving on the first pre-synthesized powder, and then carrying out secondary pre-sintering treatment to obtain second pre-synthesized powder;
and 4, step 4: performing ball milling and drying treatment on the second pre-synthesized powder in sequence to obtain a pre-prepared mixed powder;
and 5: adding a binder into the prefabricated mixed dry powder for granulation and sieving, and then performing compression molding to obtain a ceramic green body;
step 6: carrying out isostatic pressing treatment on the ceramic green body;
and 7: and sequentially carrying out glue discharging and sintering treatment on the ceramic green body subjected to isostatic pressing treatment to obtain the BT-BM 'M' -BNT dielectric energy storage ceramic.
In an embodiment of the present invention, the ball milling process in the step 2, the step 3 and the step 4 is as follows:
the method comprises the following steps of carrying out ball milling by using absolute ethyl alcohol as a grinding aid, dioctyl phthalate as a dispersing agent and zirconia balls as a ball milling medium, wherein the mass ratio of the zirconia balls to powder is (2-3): 1, the proportion of the powder to be ball-milled to the absolute ethyl alcohol is 1 g: 0.8ml to 1.5ml, the ball milling time is 16h to 24h, and the ball milling rotating speed is 350 r/min.
In one embodiment of the present invention, in the drying process in the step 2, the step 3 and the step 4, the drying temperature is 40 ℃ to 50 ℃, and the drying time is 6h to 12 h.
In one embodiment of the present invention, in the grinding and sieving process in the step 2 and the step 3, the grinding time is 0.5h, and the sieve is 60 meshes.
In an embodiment of the present invention, the first pre-firing treatment process and the second pre-firing treatment process are both:
putting the powder to be presintered into a crucible and covering, and calcining at the constant temperature of 800-950 ℃ in the atmosphere for 3-5 h.
In one embodiment of the present invention, the step 5 comprises:
step 5.1: weighing a binder polyvinyl alcohol, dissolving the binder polyvinyl alcohol in water, and carrying out water bath to obtain a PVA solution with the concentration of 7-8%;
step 5.2: adding the PVA solution into the prefabricated mixed dry powder for granulation to obtain powder particles;
step 5.3: sieving the formed powder particles, wherein the specification of a sieve is 80-120 meshes;
step 5.4: and pressing and molding the sieved powder particles under the pressure of 4-6 Mpa to obtain a ceramic green body.
In one embodiment of the present invention, the step 6 comprises:
step 6.1: carrying out vacuum-pumping packaging treatment on the ceramic green body;
step 6.2: and (3) putting the ceramic green body subjected to vacuum packaging treatment into isostatic pressing equipment, and performing densification treatment under 150-250 Mpa.
In an embodiment of the present invention, in the step 7, the glue discharging process is: under the atmosphere, heating to 120 ℃ at the speed of 2-3 ℃/min, preserving heat for 30min, then continuously heating to 600-700 ℃ at the speed of 1.5-2.5 ℃/min, preserving heat for 2-4 h, and then naturally cooling along with the furnace;
the sintering process comprises the following steps: heating to 1150-1250 ℃ at the speed of 2-3 ℃/min in the atmosphere, calcining the blank body at constant temperature for 2-2.5 h, and naturally cooling along with the furnace to obtain the BT-BM 'M' -BNT dielectric energy storage ceramic.
Compared with the prior art, the invention has the beneficial effects that:
1. the lead-free high energy storage density ceramic material is prepared by taking BNT with great saturation polarization strength as a third component and a relaxor ferroelectric BaTiO3-Bi(M′M″)O3The BT-BM 'M' -BNT system is obtained through solid solution, and the lead-free ceramic material with high energy storage density is obviously improved under the condition of saturation polarization strength (-50 mu C/cm)2) Very low remnant polarization (<5μC/cm2) And can obtain the maximum energy storage density (-4.44J/cm) under the extremely low field intensity3)；
2. According to the preparation method of the lead-free high-energy-storage-density ceramic material, the secondary pre-sintering treatment and the tertiary ball-milling process are added on the basis of the traditional preparation process, so that the pre-synthesis reaction of the mixed powder is more sufficient, the structure of the pre-synthesized mixed powder with the perovskite structure is more uniform, the powder is more uniformly mixed, the component distribution of a subsequent ceramic sample is uniform, and the density of the ceramic is effectively improved;
3. the preparation method of the lead-free high-energy-storage-density ceramic material has the advantages that the used materials are easy to obtain, the preparation process is simple, the manufacturing cost is low, the repeatability is good by matching with the traditional ceramic preparation process, and the batch production is facilitated.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following preferred embodiments are described in detail with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a lead-free high energy storage density ceramic material according to an embodiment of the present invention;
FIG. 2 is a graph showing the results of testing the ferroelectric properties of a lead-free high energy storage density ceramic material according to a different embodiment of the present invention;
FIG. 3 is a graph showing the results of the ferroelectric property test of 0.7(0.9BT-0.1BZT) -0.3BNT provided by the embodiment of the present invention;
FIG. 4 is a graph showing the ferroelectric temperature stability test results of 0.7(0.9BT-0.1BZT) -0.3BNT provided by the embodiments of the present invention;
fig. 5 is a graph showing the results of testing the ferroelectric properties of lead-free high energy storage density ceramic materials according to another different embodiment of the present invention.
Detailed Description
In order to further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be made on a lead-free ceramic material with high energy storage density and a preparation method thereof according to the present invention with reference to the accompanying drawings and the detailed description.
The foregoing and other technical matters, features and effects of the present invention will be apparent from the following detailed description of the embodiments, which is to be read in connection with the accompanying drawings. The technical means and effects of the present invention adopted to achieve the predetermined purpose can be more deeply and specifically understood through the description of the specific embodiments, however, the attached drawings are provided for reference and description only and are not used for limiting the technical scheme of the present invention.
The embodiment provides a lead-free high energy storage density ceramic material, which has a chemical formula as follows: (1-x) [ (1-y) BaTiO3-yBi(M′M″)O3]-xBi0.5Na0.5TiO3Wherein x is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0.03 and less than or equal to 0.4, M 'is Zn, Mg, Li or Ni, and M' is Hf, Ta, Nb or Ti.
The lead-free high energy storage density ceramic material of this embodiment is prepared by using BNT with very large saturation polarization as the third component and the relaxor ferroelectric BaTiO3-Bi(M′M″)O3The BT-BM 'M' -BNT system is obtained by solid solution, the extremely low residual polarization is still kept under the condition that the saturation polarization is obviously improved, and the extremely high energy storage density can be obtained under the extremely low field intensity.
Specifically, a method for preparing a lead-free ceramic material with high energy storage density in this embodiment is described, please refer to fig. 1, where fig. 1 is a schematic flow chart of a method for preparing a lead-free ceramic material with high energy storage density according to an embodiment of the present invention, and as shown in the figure, the method for preparing a lead-free ceramic material with high energy storage density in this embodiment includes:
step 1: according to (1-x) [ (1-y) BaTiO3-yBi(M′M″)O3]-xBi0.5Na0.5TiO3In the stoichiometric ratio, a Ba-containing compound, a Ti-containing compound, a Bi-containing compound, a Na-containing compound, an M 'containing compound and an M' containing compound are prepared to obtain a mixed material, wherein x is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0.03 and less than or equal to 0.4, M 'is Zn, Mg, Li or Ni, and M' is Hf, Ta, Nb or Ti;
in this embodiment, BaCO is optionally selected as the Ba-containing compound3Powder with purity of 99.8% and Ti-containing compound selected from TiO2Powder with purity of 99.99%, Bi compound selected from Bi2O3Powder with purity of 99% and Na-containing compound selected from NaCO3The purity of the powder is 99%, and the M 'containing compound and the M' containing compound can be selected from corresponding oxide powder.
In addition, for Bi2O3Powder and NaCO3The powder needs to be weighed with an excess of 2% to compensate for volatilization during the preparation process.
Step 2: performing ball milling, drying, grinding and sieving on the mixed material in sequence, and then performing first presintering treatment to obtain first presynthesized powder;
in this example, the ball milling process was: the method comprises the following steps of carrying out ball milling by using absolute ethyl alcohol as a grinding aid, dioctyl phthalate as a dispersing agent and zirconia balls as a ball milling medium, wherein the mass ratio of the zirconia balls to powder is (2-3): 1, the proportion of the powder to be ball-milled to the absolute ethyl alcohol is 1 g: 0.8ml to 1.5ml, the ball milling time is 16h to 24h, and the ball milling rotating speed is 350 r/min.
In the drying process, the drying temperature is 40-50 ℃, the drying time is 6-12 h, and concretely, an oven is used for drying the powder.
In the grinding and sieving process, the grinding time is 0.5h, the screen is 60 meshes, and specifically, a mortar is used for grinding the powder.
The first pre-sintering treatment process comprises the following steps: putting the powder to be presintered into a crucible and covering, and calcining at the constant temperature of 800-950 ℃ in the atmosphere for 3-5 h.
In this example, after the first pre-firing treatment was completed, a mixed powder of a pre-synthesized perovskite structure was formed in the crucible.
And step 3: sequentially carrying out ball milling, drying, grinding and sieving on the first pre-synthesized powder, and then carrying out secondary pre-sintering treatment to obtain second pre-synthesized powder;
in this embodiment, the ball milling, drying, grinding, sieving and pre-sintering processes in step 3 are the same as those in step 2.
Namely, the ball milling process comprises the following steps: the method comprises the following steps of carrying out ball milling by using absolute ethyl alcohol as a grinding aid, dioctyl phthalate as a dispersing agent and zirconia balls as a ball milling medium, wherein the mass ratio of the zirconia balls to powder is (2-3): 1, the proportion of the powder to be ball-milled to the absolute ethyl alcohol is 1 g: 0.8ml to 1.5ml, the ball milling time is 16h to 24h, and the ball milling rotating speed is 350 r/min.
In the drying process, the drying temperature is 40-50 ℃, the drying time is 6h, and specifically, an oven is used for drying powder.
In the grinding and sieving process, the grinding time is 0.5h, the screen is 60 meshes, and specifically, a mortar is used for grinding the powder.
The second pre-sintering treatment process comprises the following steps: putting the powder to be presintered into a crucible and covering, and calcining at the constant temperature of 800-950 ℃ in the atmosphere for 3-5 h.
And 4, step 4: performing ball milling and drying treatment on the second pre-synthesized powder in sequence to obtain pre-prepared mixed powder;
in this embodiment, the ball milling and drying processes in step 4 are the same as those in step 2. Namely, the ball milling process comprises the following steps: the method comprises the following steps of carrying out ball milling by using absolute ethyl alcohol as a grinding aid, dioctyl phthalate as a dispersing agent and zirconia balls as a ball milling medium, wherein the mass ratio of the zirconia balls to powder is (2-3): 1, the proportion of the powder to be ball-milled to the absolute ethyl alcohol is 1 g: 0.8ml to 1.5ml, the ball milling time is 16h to 24h, and the ball milling rotating speed is 350 r/min. In the drying process, the drying temperature is 40-50 ℃, the drying time is 6h, and specifically, an oven is used for drying powder.
And 5: adding a binder into the prefabricated mixed dry powder for granulation and sieving, and then performing compression molding to obtain a ceramic green body;
specifically, step 5 comprises:
step 5.1: weighing a binder polyvinyl alcohol, dissolving the binder polyvinyl alcohol in water, and carrying out water bath to obtain a PVA solution with the concentration of 7-8%;
step 5.2: adding the PVA solution into the prefabricated mixed dry powder for granulation to obtain powder particles;
step 5.3: sieving the formed powder particles, wherein the specification of a sieve is 80-120 meshes;
step 5.4: and pressing and molding the sieved powder particles under the pressure of 4-6 Mpa to obtain a ceramic green body.
Step 6: carrying out isostatic pressing treatment on the ceramic green body;
specifically, step 6 includes:
step 6.1: carrying out vacuum-pumping packaging treatment on the ceramic green body;
step 6.2: and (3) putting the ceramic green body subjected to vacuum packaging treatment into isostatic pressing equipment, and performing densification treatment under 150-250 Mpa.
And 7: and sequentially carrying out glue discharging and sintering treatment on the ceramic green body subjected to isostatic pressing treatment to obtain the BT-BM 'M' -BNT dielectric energy storage ceramic.
In this embodiment, the glue discharging process is as follows: under the atmosphere, heating to 120 ℃ at the speed of 2-3 ℃/min, preserving heat for 30min, then continuously heating to 600-700 ℃ at the speed of 1.5-2.5 ℃/min, preserving heat for 2-4 h, and then naturally cooling along with the furnace;
the sintering process comprises the following steps: heating to 1150-1250 ℃ at the speed of 2-3 ℃/min in the atmosphere, calcining the blank body at constant temperature for 2-2.5 h, and naturally cooling along with the furnace to obtain the BT-BM 'M' -BNT dielectric energy storage ceramic.
According to the preparation method of the lead-free high-energy-storage-density ceramic material, on the basis of the traditional preparation process, the secondary pre-sintering treatment and the tertiary ball-milling process are added, so that the pre-synthesis reaction of the mixed powder is more sufficient, the structure of the mixed powder of the perovskite structure formed by pre-synthesis is more uniform, the powder is more uniformly mixed, and the component distribution of a subsequent ceramic sample is uniform and the density of the ceramic is effectively improved.
Example 1
Has a chemical formula of 0.9[0.9BaTiO3-0.1Bi(Zn0.25Ta0.5)O3]-0.1Bi0.5Na0.5TiO3The preparation of the ceramic material of (3).
Step (1): according to 0.9[0.9BaTiO3-0.1Bi(Zn0.25Ta0.5)O3]-0.1Bi0.5Na0.5TiO3The raw material BaCO is weighed according to the molar stoichiometric ratio3、TiO2、Ta2O5、ZnO、Bi2O3And NaCO3Obtaining a mixed material;
step (2): and (2) performing ball milling treatment on the mixed material obtained in the step (1) by taking absolute ethyl alcohol as a grinding aid, dioctyl phthalate (DOP) as a dispersing agent and zirconia balls with two sizes as ball milling media, wherein the dosage of the absolute ethyl alcohol is as follows: adding 0.8ml of absolute ethyl alcohol into each gram of powder to be ball-milled, wherein the mass ratio of the zirconium balls to the powder is 2: 1, ball milling time is 16h, and ball milling speed is 350 r/min;
and (3): and (3) placing the uniformly mixed powder obtained in the step (2) into a drying oven for drying treatment to obtain a mixed dry powder, wherein the drying temperature is controlled to be 40 ℃, and the drying time is 6 hours.
And (4): grinding the mixed dry powder obtained in the step (3) in a mortar for half an hour and sieving the ground dry powder by using a 60-mesh sieve;
and (5): putting the uniformly mixed powder obtained in the step (4) into a pre-sintering crucible, compacting and covering to form a closed space in the crucible, calcining at the constant temperature of 800 ℃ for 3 hours in the atmosphere, and forming pre-synthesized perovskite structure mixed powder in the crucible after calcining is finished;
and (6): performing secondary ball milling treatment on the mixed powder obtained in the step (5), wherein the process is consistent with the step (2);
and (7): putting the uniformly mixed powder obtained in the step (6) into a drying oven for drying treatment, wherein the process is consistent with the step (3);
and (8): grinding and sieving the powder obtained in the step (7), wherein the process is consistent with the process in the step (4);
and (9): performing secondary calcination treatment on the uniformly mixed powder obtained in the step (8), wherein the process is consistent with the step (5);
step (10): performing ball milling and drying treatment on the pre-synthesized powder obtained in the step (9) for three times in sequence to obtain a prefabricated mixed powder, wherein the process is consistent with the steps (2) and (3);
step (11): weighing a binder polyvinyl alcohol (PVA), dissolving the PVA in water, and carrying out water bath to obtain a PVA solution with the mass percentage concentration of 7%;
step (12): adding the PVA solution prepared in the step (11) into the prefabricated mixed powder obtained in the step (10) for granulation treatment to obtain powder particles
Step (13): sieving the formed powder particles, and removing the powder particles with larger particle size, wherein the particle size of the powder particles is 80-120 meshes;
step (14): pre-pressing the powder particles obtained after sieving in the step (13) under the pressure of 4Mpa to obtain a ceramic green body;
step (15): vacuumizing and packaging the ceramic green sheet formed in the step (14), putting the ceramic green sheet into isostatic pressing equipment, and performing densification treatment under 150 Mpa;
step (16): and (5) carrying out glue discharging on the blank obtained in the step (15), wherein the specific process is as follows: heating to 120 ℃ at the speed of 2 ℃/min in the atmosphere, mainly removing water in granulation, preserving heat for 30min, then continuously heating to 600 ℃ at the slow speed of 1.5 ℃/min, and preserving heat for 2h to obtain a ceramic blank after rubber removal;
step (17): embedding the ceramic green body subjected to binder removal treatment in a muffle furnace, heating the muffle furnace to 1235 ℃ at the speed of 2 ℃/min in the atmosphere, and calcining at constant temperature for 2h to obtain 0.9[0.9BaTiO3-0.1Bi(Zn0.25Ta0.5)O3]-0.1Bi0.5Na0.5TiO3And is marked as 0.9(0.9BT-0.1BZT) -0.1 BNT.
Example 2
Has a chemical formula of 0.8[0.9BaTiO3-0.1Bi(Zn0.25Ta0.5)O3]-0.2Bi0.5Na0.5TiO3The ceramic material of (1) was prepared, wherein the sintering temperature was 1220 ℃, and the remaining preparation process was the same as in example 1 and was designated as 0.8(0.9BT-0.1BZT) -0.2 BNT.
Example 3
Has a chemical formula of 0.7[0.9BaTiO3-0.1Bi(Zn0.25Ta0.5)O3]-0.3Bi0.5Na0.5TiO3The ceramic material of (1) was prepared at a sintering temperature of 1200 ℃ and the remaining preparation process was the same as in example 1 and was designated as 0.7(0.9BT-0.1BZT) -0.3 BNT.
Example 4
Has a chemical formula of 0.6[0.9BaTiO3-0.1Bi(Zn0.25Ta0.5)O3]-0.4Bi0.5Na0.5TiO3The ceramic material of (1) was prepared at a sintering temperature of 1150 ℃ and the remaining preparation process was the same as in example 1 and was designated as 0.6(0.9BT-0.1BZT) -0.4 BNT.
Comparative example 1
Chemical formula of 0.9BaTiO3-0.1Bi(Zn0.25Ta0.5)O3The ceramic material of (1) was prepared, wherein the sintering temperature was 1250 ℃, and the remaining preparation process was the same as in example 1 and is marked as 0.9BT-0.1 BZT.
Example 5
Has a chemical formula of 0.9[0.85BaTiO3-0.15Bi(Mg 0.5Hf0.5)O3]-0.1Bi0.5Na0.5TiO3The preparation of the ceramic material of (3).
Step (1): according to 0.9[0.85BaTiO3-0.15Bi(Mg 0.5Hf0.5)O3]-0.1Bi0.5Na0.5TiO3The raw material BaCO is weighed according to the molar stoichiometric ratio3、TiO2、HfO2、MgO、Bi2O3And NaCO3Obtaining a mixed material;
step (2): and (2) performing ball milling treatment on the mixed material obtained in the step (1) by taking absolute ethyl alcohol as a grinding aid, dioctyl phthalate (DOP) as a dispersing agent and zirconia balls with two sizes as ball milling media, wherein the dosage of the absolute ethyl alcohol is as follows: adding 1.5ml of absolute ethyl alcohol into each gram of powder to be ball-milled, wherein the mass ratio of the zirconium balls to the powder is 3: 1, ball milling time is 24 hours, and ball milling speed is 350 r/min;
and (3): and (3) placing the uniformly mixed powder obtained in the step (2) into a drying oven for drying treatment to obtain a mixed dry powder, wherein the drying temperature is controlled to be 50 ℃, and the drying time is 6-12 h.
And (4): grinding the mixed dry powder obtained in the step (3) in a mortar for half an hour and sieving the ground dry powder by using a 60-mesh sieve;
and (5): putting the uniformly mixed powder obtained in the step (4) into a pre-sintering crucible, compacting and covering to form a closed space in the crucible, calcining at constant temperature of 950 ℃ in atmospheric atmosphere for 5 hours, and forming pre-synthesized perovskite structure mixed powder in the crucible after calcining is finished;
and (6): performing secondary ball milling treatment on the mixed powder obtained in the step (5), wherein the process is consistent with the step (2);
and (7): putting the uniformly mixed powder obtained in the step (6) into a drying oven for drying treatment, wherein the process is consistent with the step (3);
and (8): grinding and sieving the powder obtained in the step (7), wherein the process is consistent with the process in the step (4);
and (9): performing secondary calcination treatment on the uniformly mixed powder obtained in the step (8), wherein the process is consistent with the step (5);
step (10): performing ball milling and drying treatment on the pre-synthesized powder obtained in the step (9) for three times in sequence to obtain a prefabricated mixed powder, wherein the process is consistent with the steps (2) and (3);
step (11): weighing a binder polyvinyl alcohol (PVA), dissolving the PVA in water, and carrying out water bath to obtain a PVA solution with the mass percentage concentration of 8%;
step (12): adding the PVA solution prepared in the step (11) into the prefabricated mixed powder obtained in the step (10) for granulation treatment to obtain powder particles
Step (13): sieving the formed powder particles, and removing the powder particles with larger particle size, wherein the particle size of the powder particles is 80-120 meshes;
step (14): pre-pressing the powder particles obtained after sieving in the step (13) under the pressure of 6Mpa to obtain a ceramic green body;
step (15): vacuumizing and packaging the ceramic green sheet formed in the step (14), putting the ceramic green sheet into isostatic pressing equipment, and performing densification treatment under 250 Mpa;
step (16): and (5) carrying out glue discharging on the blank obtained in the step (15), wherein the specific process is as follows: heating to 120 ℃ at the speed of 3 ℃/min in the atmosphere, mainly removing water in granulation, preserving heat for 30min, then continuously heating to 700 ℃ at the slow speed of 2.5 ℃/min, and preserving heat for 4h to obtain a ceramic blank after rubber removal;
step (17): embedding the ceramic green body subjected to binder removal treatment in a muffle furnace, heating the muffle furnace to 1235 ℃ at the speed of 3 ℃/min in the atmosphere, and calcining at constant temperature for 2h to obtain 0.9[0.85BaTiO3-0.15Bi(Mg0.5Hf0.5)O3]-0.1Bi0.5Na0.5TiO3And is recorded as 0.9(0.85BT-0.15BMH) -0.1 BNT.
Example 6
Has a chemical formula of 0.8[0.85BaTiO3-0.15Bi(Mg 0.5Hf0.5)O3]-0.2Bi0.5Na0.5TiO3The ceramic material of (1) was prepared, wherein the sintering temperature was 1220 ℃ and the remaining preparation process was the same as in example 5 and was designated as 0.8(0.85BT-0.15BMH) -0.2 BNT.
Example 7
Has a chemical formula of 0.7[0.85BaTiO3-0.15Bi(Mg 0.5Hf0.5)O3]-0.3Bi0.5Na0.5TiO3The ceramic material of (1) was prepared at a sintering temperature of 1200 ℃ and the remaining preparation process was the same as in example 5 and was designated 0.7(0.85BT-0.15BMH) -0.3 BNT.
Example 8
Has a chemical formula of 0.6[0.85BaTiO3-0.15Bi(Mg 0.5Hf0.5)O3]-0.4Bi0.5Na0.5TiO3The ceramic material of (1) was prepared at a sintering temperature of 1150 ℃ and the same preparation process as in example 5 was carried out, and it was designated 0.6(0.85BT-0.15BMH) -0.4 BNT.
Comparative example 2
BaTiO of the chemical formula 0.853-0.15Bi(Mg 0.5Hf0.5)O3The ceramic material of (1) was prepared, wherein the sintering temperature was 1250 ℃, and the remaining preparation process was the same as in example 5 and is marked as 0.85BT-0.15 BZT.
The ferroelectric properties of the ceramic samples of examples 1-8 and comparative examples 1-2 were tested to illustrate the properties of the lead-free high energy storage density ceramic material of the present invention.
Before ferroelectric performance test, the ceramic wafer prepared in each embodiment and comparative example needs to be silver-treated, and the method specifically comprises the following steps:
step a, using 240-mesh sand paper to perform upper and lower surface thinning treatment on the ceramic wafer obtained by calcination in a polishing machine until the thickness is about 0.15 mm;
b, polishing the thinned ceramic wafer on a polishing machine by using the suspension;
c, suspending the polished ceramic wafer in a beaker, adding absolute ethyl alcohol, and ultrasonically cleaning for 10min in an ultrasonic cleaner;
and d, screen-printing the upper surface and the lower surface of the ceramic wafer subjected to ultrasonic cleaning with a low-temperature silver electrode with the diameter of 2mm, and then putting the ceramic wafer into an oven for drying, wherein the temperature of the oven is controlled to be 150 ℃, and the drying time is 30 min.
The ferroelectric properties of the ceramic samples of examples 1 to 4 and comparative example 1 after being treated with silver were tested, please refer to fig. 2, fig. 2 is a graph of the ferroelectric property test results of the lead-free high energy storage density ceramic material with different components provided in the examples of the present invention, and the energy storage performance of the lead-free high energy storage density ceramic material is calculated by using the test results, and the energy storage density and the energy storage efficiency can be calculated by the following formulas:
Figure BDA0003343648960000151
Figure BDA0003343648960000161
referring to table 1 in combination, table 1 is a result of calculation of energy storage performance of the ceramic samples of examples 1 to 4 and comparative example 1.
TABLE 1 calculation of energy storage Performance of ceramic samples
Figure BDA0003343648960000162
As can be seen from Table 1, along with the third component Bi0.5Na0.5TiO3The content of Bi is increased continuously under the condition of applying the same field intensity of 100kV/cm0.5Na0.5TiO3When the content of each component is 0-0.3, the corresponding maximum polarization intensity is continuously increased while the extremely low residual polarization intensity is kept, but the energy storage efficiency of the component with the content of 0.4 is too low, the energy loss is too high, and the requirement of practical application is not met. This means that, at a certain suitable ratio (x ═ 0.3,), the 0.7(0.9BT-0.1BZT) -0.3BNT prepared in example 3 can achieve very high energy storage densities (4.44J/cm) at relatively low field strengths (230kV/cm)3) And energy storage efficiency (88.10%), as shown in FIG. 3, FIG. 3 is the present inventionThe graph shows the ferroelectric property test results of 0.7(0.9BT-0.1BZT) -0.3BNT provided in the examples.
In addition, temperature is a key factor for evaluating the application of energy storage ceramics in complex environments, and in practical application, as a dielectric energy storage material, the dielectric energy storage ceramic not only needs to have high energy storage density, but also needs to have high energy storage efficiency. Because if the energy storage efficiency is too low, most of the stored energy is released in the form of heat during the release process, which reduces the service life and other properties of the material. Referring to fig. 4, fig. 4 is a graph showing the ferroelectric temperature stability test results of 0.7(0.9BT-0.1BZT) -0.3BNT provided by the embodiment of the present invention, wherein (a) is a P-E curve of the example at the same frequency of 1Hz and the same electric field of 120kV/cm, it can be clearly seen that Pmax is almost constant with the temperature increase, which indicates that the example has excellent ferroelectric temperature stability at 20-190 ℃; (b) the graph is a comparison graph of energy storage density and energy storage efficiency at different temperatures calculated according to the formula (1) and the formula (2) under 120kV/cm, and it can be seen that the energy storage density is kept at nearly 1.5J/cm along with the temperature rise3However, the loss is increased, and the energy storage efficiency is slightly reduced. As shown in FIG. 4, the 0.7(0.9BT-0.1BZT) -0.3BNT ceramic material has excellent ferroelectric temperature stability at 20-190 deg.C and high energy storage density (-1.5J/cm)3) The energy storage efficiency is still more than 80%.
The ferroelectric properties of the ceramic samples of examples 5 to 8 and comparative example 2 after being treated with silver were tested, and referring to fig. 5, fig. 5 is a graph showing the ferroelectric properties test results of the lead-free high energy storage density ceramic material of another different example provided by the example of the present invention. As shown, it can be seen that the BT-BMH-BNT ceramic has a common phenomenon compared with the BT-BZT-BNT ceramic: namely, with the increase of the BNT content of the third component, under the same field intensity, the corresponding maximum polarization intensity can be effectively improved on the premise of extremely low residual polarization intensity, so that higher energy storage density can be realized under very low field intensity.
The BT-BM 'M' -BNT lead-free high-energy-storage-density ceramic material prepared by the method can be applied to the fields of medical operation laser, directional energy weapons, ignition devices, hybrid electric vehicles and the like which have higher requirements on energy storage density and efficiency, and is beneficial to solving the problem of continuous development in the fields of automobile industry, aerospace, geological and petroleum exploration and the like.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or device that comprises a list of elements does not include only those elements but may include other elements not expressly listed. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of additional like elements in the article or device comprising the element.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (9)

1. A lead-free high energy storage density ceramic material is characterized in that the chemical formula of the lead-free high energy storage density ceramic material is as follows: (1-x) [ (1-y) BaTiO3-yBi(M′M″)O3]-xBi0.5Na0.5TiO3Wherein x is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0.03 and less than or equal to 0.4, M 'is Zn, Mg, Li or Ni, and M' is Hf, Ta, Nb or Ti.
2. The preparation method of the lead-free high energy storage density ceramic material is characterized by comprising the following steps:
step 1: according to (1-x) [ (1-y) BaTiO3-yBi(M′M″)O3]-xBi0.5Na0.5TiO3Medium stoichiometric ratioPreparing a Ba-containing compound, a Ti-containing compound, a Bi-containing compound, a Na-containing compound, an M '-containing compound and an M' containing compound to obtain a mixed material, wherein x is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0.03 and less than or equal to 0.4, M 'is Zn, Mg, Li or Ni, and M' is Hf, Ta, Nb or Ti;
step 2: sequentially carrying out ball milling, drying, grinding and sieving on the mixed material, and then carrying out first presintering treatment to obtain first presynthesized powder;
and step 3: sequentially carrying out ball milling, drying, grinding and sieving on the first pre-synthesized powder, and then carrying out secondary pre-sintering treatment to obtain second pre-synthesized powder;
and 4, step 4: performing ball milling and drying treatment on the second pre-synthesized powder in sequence to obtain a pre-prepared mixed powder;
and 5: adding a binder into the prefabricated mixed dry powder for granulation and sieving, and then performing compression molding to obtain a ceramic green body;
step 6: carrying out isostatic pressing treatment on the ceramic green body;
and 7: and sequentially carrying out glue discharging and sintering treatment on the ceramic green body subjected to isostatic pressing treatment to obtain the BT-BM 'M' -BNT dielectric energy storage ceramic.
3. The method for preparing the lead-free ceramic material with high energy storage density according to claim 2, wherein the ball milling process in the step 2, the step 3 and the step 4 comprises the following steps:
the method comprises the following steps of carrying out ball milling by using absolute ethyl alcohol as a grinding aid, dioctyl phthalate as a dispersing agent and zirconia balls as a ball milling medium, wherein the mass ratio of the zirconia balls to powder is (2-3): 1, the proportion of the powder to be ball-milled to the absolute ethyl alcohol is 1 g: 0.8ml to 1.5ml, the ball milling time is 16h to 24h, and the ball milling rotating speed is 350 r/min.
4. The method for preparing the lead-free ceramic material with high energy storage density according to claim 2, wherein in the drying process in the step 2, the step 3 and the step 4, the drying temperature is 40-50 ℃ and the drying time is 6-12 h.
5. The method for preparing the lead-free ceramic material with high energy storage density as claimed in claim 2, wherein in the grinding and sieving process in the step 2 and the step 3, the grinding time is 0.5h, and the sieve is 60 meshes.
6. The method for preparing the lead-free ceramic material with high energy storage density according to claim 2, wherein the first pre-sintering treatment process and the second pre-sintering treatment process are both as follows:
putting the powder to be presintered into a crucible and covering, and calcining at the constant temperature of 800-950 ℃ in the atmosphere for 3-5 h.
7. The method for preparing the lead-free ceramic material with high energy storage density as claimed in claim 2, wherein the step 5 comprises:
step 5.1: weighing a binder polyvinyl alcohol, dissolving the binder polyvinyl alcohol in water, and carrying out water bath to obtain a PVA solution with the concentration of 7-8%;
step 5.2: adding the PVA solution into the prefabricated mixed dry powder for granulation to obtain powder particles;
step 5.3: sieving the formed powder particles, wherein the specification of a sieve is 80-120 meshes;
step 5.4: and pressing and molding the sieved powder particles under the pressure of 4-6 Mpa to obtain a ceramic green body.
8. The method for preparing the lead-free ceramic material with high energy storage density as claimed in claim 2, wherein the step 6 comprises:
step 6.1: carrying out vacuum-pumping packaging treatment on the ceramic green body;
step 6.2: and (3) putting the ceramic green body subjected to vacuum packaging treatment into isostatic pressing equipment, and performing densification treatment under 150-250 Mpa.
9. The method for preparing the lead-free ceramic material with high energy storage density according to claim 2, wherein in the step 7, the glue discharging process comprises the following steps: under the atmosphere, heating to 120 ℃ at the speed of 2-3 ℃/min, preserving heat for 30min, then continuously heating to 600-700 ℃ at the speed of 1.5-2.5 ℃/min, preserving heat for 2-4 h, and then naturally cooling along with the furnace;
the sintering process comprises the following steps: heating to 1150-1250 ℃ at the speed of 2-3 ℃/min in the atmosphere, calcining the blank body at constant temperature for 2-2.5 h, and naturally cooling along with the furnace to obtain the BT-BM 'M' -BNT dielectric energy storage ceramic.
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