CN113999004B - Leadless high energy storage density ceramic material and preparation method thereof - Google Patents

Leadless high energy storage density ceramic material and preparation method thereof Download PDF

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CN113999004B
CN113999004B CN202111315942.5A CN202111315942A CN113999004B CN 113999004 B CN113999004 B CN 113999004B CN 202111315942 A CN202111315942 A CN 202111315942A CN 113999004 B CN113999004 B CN 113999004B
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energy storage
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high energy
storage density
ceramic material
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CN113999004A (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 non-ferrous metal alloyThe chemical formula of the lead-free high energy storage density ceramic material is as follows: (1-x) [ (1-y) BaTiO 3 ‑yBi(M′M″)O 3 ]‑xBi 0.5 Na 0.5 TiO 3 Wherein x is more than or equal to 0.1 and less than or equal to 0.5,0.03, y is more 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 the invention uses BNT with very large saturation polarization as a third component and relaxor ferroelectric BaTiO 3 ‑Bi(M′M″)O 3 The lead-free high energy storage density ceramic material of the invention still maintains extremely low residual polarization intensity under the condition of remarkably improving the saturation polarization intensity of the ceramic material, and can obtain extremely high energy storage density under extremely low field intensity.

Description

Leadless 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 novel renewable energy storage and utilization and electronic information technology, energy storage medium materials play an increasingly important role in various electronic and electric 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 and discharge rate), has very high cycle life and safety, and is widely applied to the fields of nuclear physics technology, medical operation laser, directional energy weapon and the like, thereby becoming 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 medium capacitor cannot meet the increasing demands of society, and the development of medium materials with high energy storage characteristics is strategically necessary.
The dielectric materials currently applied to the energy storage dielectric capacitor mainly comprise five main categories of polymers, ceramic-polymer composite materials, glass ceramics and ceramics. The dielectric ceramic has high comprehensive properties such as medium breakdown field strength, lower 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 medium capacitor. Dielectric ceramics can be generally classified into ferroelectric ceramics, antiferroelectric ceramics, linear dielectric ceramics, and relaxor ferroelectric ceramics. The relaxation ferroelectric has a gentle dielectric peak due to the existence of dispersion phase transition, namely has good temperature stability; meanwhile, the relaxation ferroelectric material has a thin and long ferroelectric hysteresis loop like an antiferroelectric material, releases more energy, has lower energy loss, and has the characteristics of higher energy storage density and energy storage efficiency.
However, the existing relaxation ferroelectric energy storage material system has the problems of low maximum saturation polarization intensity, low energy storage density caused by medium dielectric breakdown field intensity, and the practical application field of the relaxation ferroelectric energy storage material system is seriously hindered.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a lead-free ceramic material with high energy storage density and a preparation method thereof. The technical problems to be solved by the invention are realized by the following technical scheme:
the invention provides a lead-free high energy storage density ceramic material, which has the chemical formula: (1-x) [ (1-y) BaTiO 3 -yBi(M′M″)O 3 ]-xBi 0.5 Na 0.5 TiO 3 Wherein x is more than or equal to 0.1 and less than or equal to 0.5,0.03, y is more 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) BaTiO 3 -yBi(M′M″)O 3 ]-xBi 0.5 Na 0.5 TiO 3 In stoichiometric ratio, and preparing Ba-containing compound, ti-containing compound, bi-containing compound and Bi-containing compoundNa compound, M 'compound and M' compound, wherein x is more than or equal to 0.1 and less than or equal to 0.5,0.03 and y is more than or equal to 0.4, M 'is Zn, mg, li or Ni, and M' is Hf, ta, nb or Ti;
step 2: sequentially performing ball milling, drying, grinding and sieving on the mixed material, and performing first presintering treatment to obtain first presynthesized powder;
step 3: sequentially ball milling, drying, grinding and sieving the first presynthesized powder, and then performing second presintering treatment to obtain second presynthesized powder;
step 4: sequentially performing ball milling and drying treatment on the second pre-synthesized powder to obtain pre-prepared mixed powder;
step 5: adding a binder into the prefabricated mixed dry powder for granulating, sieving, and then performing compression molding to obtain a ceramic green body;
step 6: carrying out isostatic pressing treatment on the ceramic green body;
step 7: and sequentially performing 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 one embodiment of the present invention, the ball milling process in the step 2, the step 3 and the step 4 is as follows:
taking absolute ethyl alcohol as a grinding aid, dioctyl phthalate as a dispersing agent and zirconia balls as a ball milling medium for ball milling, wherein the mass ratio of the zirconia balls to the powder is (2-3): 1, the proportion of the powder to be ball-milled to the absolute ethyl alcohol is 1g:0.8ml-1.5ml, the ball milling time is 16h-24h, and the ball milling rotating speed is 350r/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 12h.
In one embodiment of the present invention, in the grinding and sieving process in the step 2 and the step 3, the grinding duration is 0.5h, and the mesh screen is 60 mesh.
In one embodiment of the present invention, the first burn-in process and the second burn-in process are each:
placing the powder to be pre-burned into a crucible, covering, and calcining at constant temperature of 800-950 ℃ in the atmosphere for 3-5 h.
In one embodiment of the present invention, the step 5 includes:
step 5.1: weighing binder polyvinyl alcohol, dissolving the binder polyvinyl alcohol in water, and obtaining PVA solution with the concentration of 7% -8% in a water bath;
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 the 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 the ceramic green body.
In one embodiment of the present invention, the step 6 includes:
step 6.1: carrying out vacuumizing packaging treatment on the ceramic green body;
step 6.2: and (3) placing the ceramic green body subjected to vacuum packaging treatment into isostatic pressing equipment, and carrying out densification treatment under 150-250 Mpa.
In one embodiment of the present invention, in the step 7, the glue discharging process is: heating to 120 ℃ at the speed of 2 ℃/min-3 ℃/min under the atmosphere, preserving heat for 30min, then continuously heating to 600 ℃ to 700 ℃ at the speed of 1.5 ℃/min-2.5 ℃/min, preserving heat for 2h-4h, and then naturally cooling along with a furnace;
the sintering process comprises the following steps: heating to 1150-1250 ℃ at a speed of 2-3 ℃/min under the atmosphere, calcining the blank body at constant temperature for 2-2.5 h, and naturally cooling with a 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 of the invention uses BNT with very large saturation polarization as a third component and relaxor ferroelectric BaTiO 3 -Bi(M′M″)O 3 Solid solution is carried out to obtain a BT-BM 'M' -BNT system, and the leadless high energy storage density ceramic of the inventionThe material has a saturation polarization of (-50 mu C/cm) 2 ) Still keep extremely low residual polarization intensity<5μC/cm 2 ) And can obtain extremely high energy storage density (-4.44J/cm) under extremely low field intensity 3 )；
2. According to the preparation method of the leadless high-energy-storage-density ceramic material, on the basis of the traditional preparation process, the secondary presintering treatment and the tertiary ball milling process are added, so that the presynthesis reaction of the mixed powder is more complete, the structure of the mixed powder with a perovskite structure formed by presynthesis is more uniform, the powder is more uniformly mixed, the components of the subsequent ceramic sample are uniformly distributed, and the compactness of the ceramic is effectively improved;
3. the preparation method of the leadless high energy storage density ceramic material has the advantages of easy acquisition of the used materials, simple preparation process, low manufacturing cost, good repeatability and suitability for batch production, and is matched with the traditional ceramic preparation process.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention, as well as the preferred embodiments thereof, together with the following detailed description of the invention, given by way of illustration only, together with the accompanying drawings.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a lead-free high energy storage density ceramic material provided by the embodiment of the invention;
FIG. 2 is a graph of ferroelectric performance test results of a different embodiment of a lead-free high energy storage density ceramic material provided by an embodiment of the present invention;
FIG. 3 is a graph showing the results of ferroelectric performance tests of 0.7 (0.9 BT-0.1 BZT) -0.3BNT provided by the examples of the present invention;
FIG. 4 is a graph showing the results of a ferroelectric temperature stability test of 0.7 (0.9 BT-0.1 BZT) -0.3BNT provided by an embodiment of the present invention;
fig. 5 is a graph of ferroelectric property test results of a lead-free high energy storage density ceramic material according to another embodiment of the present invention.
Detailed Description
In order to further illustrate the technical means and effects adopted by the invention to achieve the preset aim, the invention provides a lead-free high energy storage density ceramic material and a preparation method thereof, and the lead-free high energy storage density ceramic material and the preparation method thereof are described in detail below with reference to the accompanying drawings and the detailed description.
The foregoing and other features, aspects, and advantages of the present invention will become more apparent from the following detailed description of the preferred embodiments when taken in conjunction with the accompanying drawings. The technical means and effects adopted by the present invention to achieve the intended 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 intended to limit the technical scheme of the present invention.
The embodiment provides a leadless high energy storage density ceramic material, which has a chemical formula as follows: (1-x) [ (1-y) BaTiO 3 -yBi(M′M″)O 3 ]-xBi 0.5 Na 0.5 TiO 3 Wherein x is more than or equal to 0.1 and less than or equal to 0.5,0.03, y is more 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 the embodiment uses BNT with great saturation polarization as a third component and relaxor ferroelectric BaTiO 3 -Bi(M′M″)O 3 And 3, carrying out solid solution to obtain a BT-BM 'M' -BNT system, wherein the residual polarization intensity is extremely low under the condition that the saturation polarization intensity is remarkably improved, and the energy storage density can be extremely high under extremely low field intensity.
Specifically, referring to fig. 1 for a description of a method for preparing a leadless high energy storage density ceramic material according to this embodiment, fig. 1 is a schematic flow chart of a method for preparing a leadless high energy storage density ceramic material according to an embodiment of the invention, where the method for preparing a leadless high energy storage density ceramic material according to this embodiment includes:
step 1: according to (1-x) [ (1-y) BaTiO 3 -yBi(M′M″)O 3 ]-xBi 0.5 Na 0.5 TiO 3 In stoichiometric ratio, and preparing Ba-containing compound, ti-containing compound, bi-containing compound and Na-containing compoundObtaining a mixed material, wherein x is more than or equal to 0.1 and less than or equal to 0.5,0.03, y is more than or equal to 0.4, M 'is Zn, mg, li or Ni, and M' is Hf, ta, nb or Ti;
in this embodiment, the Ba-containing compound is selected from BaCO 3 The purity of the powder is 99.8%, and the Ti-containing compound is TiO 2 The purity of the powder is 99.99%, and the Bi-containing compound is Bi 2 O 3 The purity of the powder is 99%, and the Na-containing compound is NaCO 3 The purity of the powder is 99%, and the M 'containing compound and the M' containing compound can be selected from corresponding oxide powder.
In the case of Bi 2 O 3 Powder and NaCO 3 The powder is weighed with an excess of 2% to compensate for the volatilization during the preparation process.
Step 2: sequentially performing ball milling, drying, grinding and sieving on the mixed materials, and performing first presintering treatment to obtain first presynthesized powder;
in this example, the ball milling process was: taking absolute ethyl alcohol as a grinding aid, dioctyl phthalate as a dispersing agent and zirconia balls as a ball milling medium for ball milling, wherein the mass ratio of the zirconia balls to the powder is (2-3): 1, the proportion of the powder to be ball-milled to the absolute ethyl alcohol is 1g:0.8ml-1.5ml, the ball milling time is 16h-24h, and the ball milling rotating speed is 350r/min.
In the drying process, the temperature of drying is 40-50 ℃ and the drying time is 6-12 h, and specifically, the powder is dried by using an oven.
In the grinding and sieving process, the grinding time is 0.5h, the screen is 60 mesh, and specifically, the powder is ground by using a mortar.
The first presintering treatment process comprises the following steps: placing the powder to be pre-burned into a crucible, covering, and calcining at constant temperature of 800-950 ℃ in the atmosphere for 3-5 h.
In this example, after the completion of the first pre-firing treatment, a mixed powder of a pre-synthesized perovskite structure was formed in the crucible.
Step 3: sequentially performing ball milling, drying, grinding and sieving on the first presynthesized powder, and performing second presintering treatment to obtain second presynthesized powder;
in this example, the ball milling, baking, grinding and sieving process in step 3 is identical to that in step 2.
Namely, the ball milling process is as follows: taking absolute ethyl alcohol as a grinding aid, dioctyl phthalate as a dispersing agent and zirconia balls as a ball milling medium for ball milling, wherein the mass ratio of the zirconia balls to the powder is (2-3): 1, the proportion of the powder to be ball-milled to the absolute ethyl alcohol is 1g:0.8ml-1.5ml, the ball milling time is 16h-24h, and the ball milling rotating speed is 350r/min.
In the drying process, the temperature of drying is 40-50 ℃ and the drying time is 6 hours, and specifically, the powder is dried by using an oven.
In the grinding and sieving process, the grinding time is 0.5h, the screen is 60 mesh, and specifically, the powder is ground by using a mortar.
The second presintering treatment process comprises the following steps: placing the powder to be pre-burned into a crucible, covering, and calcining at constant temperature of 800-950 ℃ in the atmosphere for 3-5 h.
Step 4: sequentially performing ball milling and drying treatment on the second pre-synthesized powder to obtain pre-prepared mixed powder;
in this example, the ball milling and drying process in step 4 is identical to that in step 2. Namely, the ball milling process is as follows: taking absolute ethyl alcohol as a grinding aid, dioctyl phthalate as a dispersing agent and zirconia balls as a ball milling medium for ball milling, wherein the mass ratio of the zirconia balls to the powder is (2-3): 1, the proportion of the powder to be ball-milled to the absolute ethyl alcohol is 1g:0.8ml-1.5ml, the ball milling time is 16h-24h, and the ball milling rotating speed is 350r/min. In the drying process, the temperature of drying is 40-50 ℃ and the drying time is 6 hours, and specifically, the powder is dried by using an oven.
Step 5: adding a binder into the prefabricated mixed dry powder for granulating and sieving, and then, performing compression molding to obtain a ceramic green body;
specifically, step 5 includes:
step 5.1: weighing binder polyvinyl alcohol, dissolving the binder polyvinyl alcohol in water, and obtaining PVA solution with the concentration of 7% -8% in a water bath;
step 5.2: adding 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 the 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 the ceramic green body.
Step 6: carrying out isostatic pressing treatment on the ceramic green body;
specifically, step 6 includes:
step 6.1: vacuumizing and packaging the ceramic green body;
step 6.2: and (3) placing the ceramic green body subjected to vacuum packaging treatment into isostatic pressing equipment, and carrying out densification treatment under 150-250 Mpa.
Step 7: and sequentially performing 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: heating to 120 ℃ at the speed of 2 ℃/min-3 ℃/min under the atmosphere, preserving heat for 30min, then continuously heating to 600 ℃ to 700 ℃ at the speed of 1.5 ℃/min-2.5 ℃/min, preserving heat for 2h-4h, and then naturally cooling along with a furnace;
the sintering process comprises the following steps: heating to 1150-1250 ℃ at a speed of 2-3 ℃/min under the atmosphere, calcining the blank body at constant temperature for 2-2.5 h, and naturally cooling with a furnace to obtain the BT-BM 'M' -BNT dielectric energy storage ceramic.
According to the preparation method of the leadless high-energy-storage-density ceramic material, on the basis of a traditional preparation process, the secondary presintering treatment and the tertiary ball milling process are added, so that the presynthesis reaction of the mixed powder is more sufficient, the structure of the mixed powder with a perovskite structure formed by presynthesis is more uniform, the powder is more uniformly mixed, the components of a subsequent ceramic sample are uniformly distributed, and the compactness of the ceramic is effectively improved.
Example 1
Chemical formula is 0.9[0.9 ]BaTiO 3 -0.1Bi(Zn 0.25 Ta 0.5 )O 3 ]-0.1Bi 0.5 Na 0.5 TiO 3 Is prepared from the ceramic material.
Step (1): according to 0.9[0.9BaTiO ] 3 -0.1Bi(Zn 0.25 Ta 0.5 )O 3 ]-0.1Bi 0.5 Na 0.5 TiO 3 Is prepared by weighing BaCO 3 、TiO 2 、Ta 2 O 5 、ZnO、Bi 2 O 3 And NaCO 3 Obtaining a mixed material;
step (2): taking absolute ethyl alcohol as a grinding aid, dioctyl phthalate (DOP) as a dispersing agent, taking zirconia balls with two sizes as ball milling media, and carrying out ball milling treatment on the mixed material obtained in the step (1), 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 zirconium balls to powder is 2:1, the ball milling time is 16 hours, and the ball milling rotating speed is 350r/min;
step (3): and (3) placing the uniform mixed powder obtained in the step (2) into an oven for drying treatment to obtain mixed dry powder, wherein the drying temperature is controlled to be 40 ℃, and the drying time is 6 hours.
Step (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 a 60-mesh screen;
step (5): placing the uniform mixed powder obtained in the step (4) into a presintering crucible, compacting and capping to form a closed space in the crucible, calcining at a constant temperature of 800 ℃ in an atmosphere for 3 hours, and forming presynthesized perovskite structure mixed powder in the crucible after the calcining is completed;
step (6): performing secondary ball milling treatment on the mixed powder obtained in the step (5), wherein the process is consistent with that in the step (2);
step (7): placing the uniform mixed powder obtained in the step (6) into an oven for drying treatment, wherein the process is consistent with the step (3);
step (8): grinding and sieving the powder obtained in the step (7), wherein the process is consistent with the step (4);
step (9): carrying out secondary calcination treatment on the uniform mixed powder obtained in the step (8), wherein the process is consistent with the step (5);
step (10): sequentially performing ball milling and drying treatment on the pre-synthesized powder obtained in the step (9) for three times to obtain pre-prepared mixed powder, wherein the process is consistent with that of the step (2) and the step (3);
step (11): weighing binder polyvinyl alcohol (PVA) and dissolving the binder polyvinyl alcohol (PVA) in water, and carrying out water bath to obtain a PVA solution with the mass percent 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, removing the powder particles with larger particle size, wherein the particle size of the powder particles is 80-120 meshes;
step (14): prepressing and molding the powder particles obtained after sieving in the step (13) under the pressure of 4Mpa to obtain ceramic green bodies;
step (15): vacuumizing and packaging the ceramic green sheet molded in the step (14), placing the ceramic green sheet into isostatic pressing equipment, and performing densification treatment under 150 Mpa;
step (16): and (3) performing glue discharging on the blank obtained in the step (15), wherein the concrete process comprises the following steps: heating to 120 ℃ at a speed of 2 ℃/min under the atmosphere, mainly removing water in the mixture during granulation, preserving heat for 30min, then continuously heating to 600 ℃ at a slow speed of 1.5 ℃/min, and preserving heat for 2h to obtain a ceramic blank after glue removal;
step (17): burying powder of ceramic green body after glue discharge treatment, placing in a muffle furnace, heating the muffle furnace to 1235 ℃ at a speed of 2 ℃/min under the atmosphere, and calcining at constant temperature for 2h to obtain 0.9[0.9BaTiO ] 3 -0.1Bi(Zn 0.25 Ta 0.5 )O 3 ]-0.1Bi 0.5 Na 0.5 TiO 3 And is designated as 0.9 (0.9 BT-0.1 BZT) -0.1BNT.
Example 2
Chemical formula is 0.8[0.9BaTiO ] 3 -0.1Bi(Zn 0.25 Ta 0.5 )O 3 ]-0.2Bi 0.5 Na 0.5 TiO 3 Wherein the sintering temperature is 1220 ℃, and the rest is madeThe preparation was the same as in example 1, denoted 0.8 (0.9 BT-0.1 BZT) -0.2BNT.
Example 3
Chemical formula is 0.7[0.9BaTiO ] 3 -0.1Bi(Zn 0.25 Ta 0.5 )O 3 ]-0.3Bi 0.5 Na 0.5 TiO 3 Wherein the sintering temperature is 1200 ℃, and the rest of the preparation process is the same as in example 1, and is recorded as 0.7 (0.9 BT-0.1 BZT) -0.3BNT.
Example 4
Chemical formula is 0.6[0.9BaTiO ] 3 -0.1Bi(Zn 0.25 Ta 0.5 )O 3 ]-0.4Bi 0.5 Na 0.5 TiO 3 Wherein the sintering temperature is 1150 ℃, and the rest of the preparation process is the same as in example 1, and is recorded as 0.6 (0.9 BT-0.1 BZT) -0.4BNT.
Comparative example 1
Chemical formula of 0.9BaTiO 3 -0.1Bi(Zn 0.25 Ta 0.5 )O 3 Wherein the sintering temperature is 1250 ℃, and the rest of the preparation process is the same as in example 1, and is recorded as 0.9BT-0.1BZT.
Example 5
Chemical formula is 0.9[0.85BaTiO ] 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 ]-0.1Bi 0.5 Na 0.5 TiO 3 Is prepared from the ceramic material.
Step (1): according to 0.9[0.85BaTiO ] 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 ]-0.1Bi 0.5 Na 0.5 TiO 3 Is prepared by weighing BaCO 3 、TiO 2 、HfO 2 、MgO、Bi 2 O 3 And NaCO 3 Obtaining a mixed material;
step (2): taking absolute ethyl alcohol as a grinding aid, dioctyl phthalate (DOP) as a dispersing agent, taking zirconia balls with two sizes as ball milling media, and carrying out ball milling treatment on the mixed material obtained in the step (1), wherein the dosage of the absolute ethyl alcohol is as follows: 1.5ml absolute ethyl alcohol is added into each gram of powder to be ball-milled, and the mass ratio of zirconium balls to powder is 3:1, ball milling time is 24 hours, and ball milling rotating speed is 350r/min;
step (3): and (3) placing the uniform mixed powder obtained in the step (2) into an oven for drying treatment to obtain mixed dry powder, wherein the drying temperature is controlled to be 50 ℃, and the drying time is 6-12 h.
Step (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 a 60-mesh screen;
step (5): placing the uniform mixed powder obtained in the step (4) into a presintering crucible, compacting and capping to form a closed space in the crucible, calcining at constant temperature of 950 ℃ in the atmosphere for 5 hours, and forming presynthesized perovskite structure mixed powder in the crucible after the calcining is completed;
step (6): performing secondary ball milling treatment on the mixed powder obtained in the step (5), wherein the process is consistent with that in the step (2);
step (7): placing the uniform mixed powder obtained in the step (6) into an oven for drying treatment, wherein the process is consistent with the step (3);
step (8): grinding and sieving the powder obtained in the step (7), wherein the process is consistent with the step (4);
step (9): carrying out secondary calcination treatment on the uniform mixed powder obtained in the step (8), wherein the process is consistent with the step (5);
step (10): sequentially performing ball milling and drying treatment on the pre-synthesized powder obtained in the step (9) for three times to obtain pre-prepared mixed powder, wherein the process is consistent with that of the step (2) and the step (3);
step (11): weighing binder polyvinyl alcohol (PVA) and dissolving the binder polyvinyl alcohol (PVA) in water, and carrying out water bath to obtain a PVA solution with the mass percent 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, removing the powder particles with larger particle size, wherein the particle size of the powder particles is 80-120 meshes;
step (14): prepressing and molding the powder particles obtained after sieving in the step (13) under the pressure of 6Mpa to obtain ceramic green bodies;
step (15): vacuumizing and packaging the ceramic green sheet molded in the step (14), placing the ceramic green sheet into isostatic pressing equipment, and performing densification treatment under 250 Mpa;
step (16): and (3) performing glue discharging on the blank obtained in the step (15), wherein the concrete process comprises the following steps: heating to 120 ℃ at a speed of 3 ℃/min under the atmosphere, mainly removing water in the mixture during granulation, preserving heat for 30min, then continuously heating to 700 ℃ at a slow speed of 2.5 ℃/min, and preserving heat for 4h to obtain a ceramic blank after glue removal;
step (17): burying powder of the ceramic green body after the glue discharging treatment, placing the ceramic green body in a muffle furnace, heating the muffle furnace to 1235 ℃ at a speed of 3 ℃/min under the atmosphere, and calcining for 2 hours at constant temperature to obtain 0.9[0.85BaTiO ] 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 ]-0.1Bi 0.5 Na 0.5 TiO 3 And is designated 0.9 (0.85 BT-0.15 BMH) -0.1BNT.
Example 6
Chemical formula is 0.8[0.85BaTiO ] 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 ]-0.2Bi 0.5 Na 0.5 TiO 3 Wherein the sintering temperature is 1220 ℃, and the rest of the preparation process is the same as in example 5, and is recorded as 0.8 (0.85 BT-0.15 BMH) -0.2BNT.
Example 7
Chemical formula is 0.7[0.85BaTiO ] 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 ]-0.3Bi 0.5 Na 0.5 TiO 3 Wherein the sintering temperature is 1200 ℃, and the rest of the preparation process is the same as in example 5, and is recorded as 0.7 (0.85 BT-0.15 BMH) -0.3BNT.
Example 8
Chemical formula is 0.6[0.85BaTiO ] 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 ]-0.4Bi 0.5 Na 0.5 TiO 3 Wherein the sintering temperature is 1150 ℃, and the rest of the preparation process is the same as in example 5, and is recorded as 0.6 (0.85 BT-0.15 BMH) -0.4BNT.
Comparative example 2
Chemical formula is 0.85BaTiO 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 Wherein the sintering temperature is 1250 ℃, and the rest of the preparation process is the same as in example 5, and is recorded as 0.85BT-0.15BZT.
The ferroelectric properties of the ceramic samples of examples 1-8 and comparative examples 1-2 were tested to demonstrate the properties of the lead-free high energy storage density ceramic materials of the present invention.
Before ferroelectric performance test, the ceramic sheets prepared in each example and comparative example need to be silver treated, and the method specifically comprises the following steps:
step a, thinning the upper and lower surfaces of the ceramic sheet obtained by calcination by using 240-mesh sand paper on a polishing machine until the thickness is about 0.15 mm;
step b, polishing the thinned ceramic wafer on a polishing machine by using suspension;
step c, suspending the polished ceramic wafer in a beaker, adding absolute ethyl alcohol, and ultrasonically cleaning in an ultrasonic cleaner for 10min;
and d, screen printing low-temperature silver electrodes with diameters of 2mm on the upper surface and the lower surface of the ceramic sheet after ultrasonic cleaning, and then drying in a drying oven, wherein the temperature of the drying oven is controlled to be 150 ℃, and the drying time is 30min.
For testing the ferroelectric properties of the ceramic samples of examples 1 to 4 and comparative example 1 after silver treatment, please refer to fig. 2, fig. 2 is a graph showing the test results of ferroelectric properties of a lead-free ceramic material with high energy storage density of different components according to the present invention, and the energy storage properties are calculated by using the test results, and the energy storage density and the energy storage efficiency are calculated by the following formula:
Figure BDA0003343648960000151
Figure BDA0003343648960000161
referring to Table 1 in combination, table 1 shows the results of calculations of the energy storage properties of the ceramic samples of examples 1-4 and comparative example 1.
TABLE 1 calculation results of energy storage Properties of ceramic samples
Figure BDA0003343648960000162
As can be seen from Table 1, following the third component Bi 0.5 Na 0.5 TiO 3 The content is increased continuously, bi is added under the condition of applying the same field intensity of 100kV/cm 0.5 Na 0.5 TiO 3 The maximum polarization intensity corresponding to each component with the content of x=0-0.3 is continuously increased while the extremely low residual polarization intensity is maintained, but the energy storage efficiency of the x=0.4 component is too low, the energy loss is too high, and the practical application requirements are not met. This means that, at a certain suitable ratio (x=0.3), i.e. 0.7 (0.9 BT-0.1 BZT) -0.3BNT prepared in example 3, a very high energy storage density (4.44J/cm) can be achieved at a relatively low field strength (230 kV/cm) 3 ) And energy storage efficiency (88.10%), as shown in fig. 3, fig. 3 is a graph of ferroelectric performance test results of 0.7 (0.9 BT-0.1 BZT) -0.3BNT provided by the embodiment of the invention.
In addition, temperature is a key factor in evaluating the application of energy storage ceramics in complex environments, and in practical applications, as a dielectric energy storage material, not only needs to have high energy storage density, but also 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, the service life of the material is reduced, as well as other properties. Referring to fig. 4, fig. 4 is a graph showing the test result of ferroelectric temperature stability of 0.7 (0.9 BT-0.1 BZT) -0.3BNT provided in 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, and it can be clearly seen that Pmax is almost unchanged with the rise of temperature, indicating 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 120kV/cm according to the formula (1) and the formula (2), and the graph can be seen as followsThe energy storage density is kept near 1.5J/cm with the rise of temperature 3 But the loss is increased and the energy storage efficiency is slightly reduced. As shown in FIG. 4, the 0.7 (0.9 BT-0.1 BZT) -0.3BNT ceramic material has excellent ferroelectric temperature stability at 20-190 ℃ and high energy storage density (-1.5J/cm) 3 ) The energy storage efficiency is 80% or more.
The ferroelectric properties of the ceramic samples of examples 5-8 and comparative example 2 after silver treatment were tested, and referring to fig. 5, fig. 5 is a graph showing the results of ferroelectric properties of lead-free high-energy-storage-density ceramic materials of another different embodiment according to the present invention. As shown in the figure, the BT-BMH-BNT ceramic shares a common phenomenon with the BT-BZT-BNT ceramic: namely, along with the increase of the BNT content of the third component, under the same field intensity, the BNT content can effectively improve the corresponding maximum polarization intensity on the premise of extremely low residual polarization intensity, thereby realizing higher energy storage density under extremely low field intensity.
The BT-BM 'M' -BNT lead-free ceramic material with high energy storage density prepared by the method can be applied to the fields of medical operation lasers, directional energy weapons, ignition devices, hybrid electric vehicles and the like with high requirements on energy storage density and efficiency, and is beneficial to solving the problem of sustainable development in the fields of automobile industry, aerospace, geology, petroleum exploration and the like.
It should be noted that in this document relational terms such as first and second, and the like are 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. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or apparatus 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 one … …" does not exclude the presence of other like elements in an article or apparatus that comprises the element.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.

Claims (9)

1. The lead-free high energy storage density ceramic material is characterized by comprising the following chemical formula: (1-x) [ (1-y) BaTiO 3 -yBi(M′M″)O 3 ]-xBi 0.5 Na 0.5 TiO 3 Wherein x is more than or equal to 0.1 and less than or equal to 0.5,0.03, y is more than or equal to 0.4, M 'is Zn, and M' is Ta;
wherein (1-x) [ (1-y) BaTiO is prepared 3 -yBi(M′M″)O 3 ]-xBi 0.5 Na 0.5 TiO 3 And (3) preparing 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 according to the stoichiometric ratio in the chemical formula to obtain a mixed material, and performing ball milling for two times and three times through presintering, granulating, tabletting and sintering to obtain the lead-free high energy storage density ceramic material.
2. The preparation method of the leadless high energy storage density ceramic material is characterized by comprising the following steps:
step 1: according to (1-x) [ (1-y) BaTiO 3 -yBi(M′M″)O 3 ]-xBi 0.5 Na 0.5 TiO 3 In 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 0.5,0.03, y is more than or equal to 0.4, M 'is Zn, and M' is Ta;
step 2: sequentially performing ball milling, drying, grinding and sieving on the mixed material, and performing first presintering treatment to obtain first presynthesized powder;
step 3: sequentially ball milling, drying, grinding and sieving the first presynthesized powder, and then performing second presintering treatment to obtain second presynthesized powder;
step 4: sequentially performing ball milling and drying treatment on the second pre-synthesized powder to obtain pre-prepared mixed powder;
step 5: adding a binder into the prefabricated mixed dry powder for granulating, sieving, and then performing compression molding to obtain a ceramic green body;
step 6: carrying out isostatic pressing treatment on the ceramic green body;
step 7: and sequentially performing 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 a lead-free high energy storage density ceramic material according to claim 2, wherein the ball milling process in the step 2, the step 3 and the step 4 is as follows:
taking absolute ethyl alcohol as a grinding aid, dioctyl phthalate as a dispersing agent and zirconia balls as a ball milling medium for ball milling, wherein the mass ratio of the zirconia balls to the powder is (2-3): 1, the proportion of the powder to be ball-milled to the absolute ethyl alcohol is 1g:0.8ml-1.5ml, the ball milling time is 16h-24h, and the ball milling rotating speed is 350r/min.
4. The method for preparing a lead-free high energy storage density ceramic material 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 ℃ to 50 ℃ and the drying time is 6h to 12h.
5. The method for preparing a lead-free high energy storage density ceramic material according to 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 screen is 60 mesh.
6. The method for preparing a lead-free high energy storage density ceramic material according to claim 2, wherein the first presintering treatment process and the second presintering treatment process are:
placing the powder to be pre-burned into a crucible, covering, and calcining at constant temperature of 800-950 ℃ in the atmosphere for 3-5 h.
7. The method for preparing a lead-free high energy storage density ceramic material according to claim 2, wherein the step 5 comprises:
step 5.1: weighing binder polyvinyl alcohol, dissolving the binder polyvinyl alcohol in water, and obtaining PVA solution with the concentration of 7% -8% in a water bath;
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 the 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 the ceramic green body.
8. The method for preparing a lead-free high energy storage density ceramic material according to claim 2, wherein the step 6 comprises:
step 6.1: carrying out vacuumizing packaging treatment on the ceramic green body;
step 6.2: and (3) placing the ceramic green body subjected to vacuum packaging treatment into isostatic pressing equipment, and carrying out densification treatment under 150-250 Mpa.
9. The method for preparing a leadless high energy storage density ceramic material according to claim 2, wherein in step 7, the glue discharging process comprises: heating to 120 ℃ at the speed of 2 ℃/min-3 ℃/min under the atmosphere, preserving heat for 30min, then continuously heating to 600 ℃ to 700 ℃ at the speed of 1.5 ℃/min-2.5 ℃/min, preserving heat for 2h-4h, and then naturally cooling along with a furnace;
the sintering process comprises the following steps: heating to 1150-1250 ℃ at a speed of 2-3 ℃/min under the atmosphere, calcining the blank body at constant temperature for 2-2.5 h, and naturally cooling with a furnace to obtain the BT-BM 'M' -BNT dielectric energy storage ceramic.
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