CN116693285A - Super-cis-electric-phase sodium bismuth titanate-based relaxation energy storage ceramic material and preparation method thereof - Google Patents
Super-cis-electric-phase sodium bismuth titanate-based relaxation energy storage ceramic material and preparation method thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 76
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 23
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012071 phase Substances 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 229910003237 Na0.5Bi0.5TiO3 Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 43
- 239000000919 ceramic Substances 0.000 claims description 38
- 238000000498 ball milling Methods 0.000 claims description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- 238000005056 compaction Methods 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims description 4
- 238000005360 mashing Methods 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000009694 cold isostatic pressing Methods 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims 1
- 230000010287 polarization Effects 0.000 abstract description 13
- 238000005452 bending Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000003989 dielectric material Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000005684 electric field Effects 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 5
- 230000014509 gene expression Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 2
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- -1 Niobium ion Chemical class 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- VNSWULZVUKFJHK-UHFFFAOYSA-N [Sr].[Bi] Chemical compound [Sr].[Bi] VNSWULZVUKFJHK-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910001460 tantalum ion Inorganic materials 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
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Abstract
The invention discloses a super-paraelectric phase bismuth sodium titanate based relaxation energy storage ceramic material and a preparation method thereof, wherein the super-paraelectric phase bismuth sodium titanate based relaxation energy storage ceramic material is prepared from a ferroelectric material component SmFeO 3 0.6Na with relaxed ferroelectric material 0.5 Bi 0.5 TiO 3 ‑0.4Sr 0.7 Bi 0.2 TiO 3 Is prepared by sintering by a solid phase reaction method, and has a chemical formula of (1-x) (0.6 Na 0.5 Bi 0.5 TiO 3 ‑0.4Sr 0.7 Bi 0.2 TiO 3 )‑xSmFeO 3 Wherein x is mole fraction, x is less than or equal to 0.05 and less than or equal to 0.15, the preparation of the superparamagnetic phase sodium bismuth titanate-based relaxation energy storage ceramic material effectively overcomes the defects of higher remnant polarization intensity and P-E curve bending in the traditional relaxation ferroelectric material,greatly improves the discharge energy density and the energy storage efficiency of the dielectric material, and the energy storage performance is obviously better than that of undoped 0.6Na 0.5 Bi 0.5 TiO 3 ‑0.4Sr 0.7 Bi 0.2 TiO 3 A relaxed ferroelectric material; the preparation method has the advantages of simple process, easily available raw materials and high production efficiency, and is suitable for large-scale practical production and application.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a super-cis-electric phase sodium bismuth titanate-based relaxation energy storage ceramic material and a preparation method thereof.
Background
The pulse power system is high in power and small in size, and an energy storage dielectric medium with excellent performance needs to be researched as a component, so that the dielectric constant of the material is high, the dielectric loss is low, and the breakdown field strength is high, and therefore the energy storage density and the energy storage efficiency of the component are high.
Currently, most of commercial energy storage materials are PbTiO 3 (PT) based material, pure PT ceramic although having a high Curie temperature T c The alloy has the characteristics of 490 ℃ but poor performance, difficult sintering, easy crack occurrence, easy volatilization of lead (Pb), environmental pollution and harm to human health, and sodium bismuth titanate (Na 0.5 Bi 0.5 TiO 3 Compared with PT, the NBT) base ceramic is environment-friendly, the raw materials are cheap, the Curie temperature of the NBT ceramic is up to 320 ℃, and the maximum polarization intensity can exceed 45 mu C/cm 2 Shows excellent energy storage potential. However, NBT has the disadvantages of low breakdown strength and high remnant polarization, and it is difficult to obtain a fine and straight hysteresis loop, resulting in poor energy storage performance.
In order to improve the energy storage performance of NBT ceramics, the preparation process is mainly optimized, elements are doped, and binary solid solutions are formed by other stable perovskite structures. The preparation process comprises the following steps: improving the sintering mode or adopting a rolling process and the like; elemental doping such as: lanthanum ion (La) 3+ ) Potassium ion (K) + ) Lithium ion (Li) + ) Doped with A-site, magnesium ion (Mg 2+ ) Niobium ion (Nb) 5+ ) Tantalum ion (Ta) 5+ ) Doping B site; with other ABO 3 Ferroelectric, e.g. strontium bismuth titanate (Sr) 0.7 Bi 0.2 TiO 3 ) Sodium niobate (NaNbO) 3 ) And calcium titanate (CaTiO) 3 ) Etc., to form solid solutions to enhance relaxation properties. Wherein Sr is 0.7 Bi 0.2 TiO 3 The introduction of the NBT material enables the perovskite structure of the NBT material to be more stable, enhances the relaxation performance and the insulation performance of the NBT matrix to a certain extent, and effectively reduces the remnant polarization intensity of the system. But the residual polarization intensity is still excessive, which is more importantHowever, the "polarization-electric field (P-E) curve" is relatively curved, severely limiting the improvement in discharge energy density and energy storage efficiency.
In addition, after a great deal of literature research on NBT relaxation energy storage ceramics, a new path for researching the energy storage density is still lacking besides the conventional methods of enhancing the polarization intensity, reducing the residual polarization and improving the breakdown strength, but a P-E curve directly related to the energy storage density is freshly researched and reported, so that researching the energy storage performance of NBT relaxation ferroelectric ceramics from the linear characteristic of the P-E curve becomes a problem with important production practice significance.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a super-cis-electric-phase sodium bismuth titanate-based relaxation energy storage ceramic material and a preparation method thereof.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows: a superparamagnetic phase bismuth sodium titanate based relaxation energy storage ceramic material is prepared from ferroelectric material component SmFeO 3 0.6Na with relaxed ferroelectric material 0.5 Bi 0.5 TiO 3 –0.4Sr 0.7 Bi 0.2 TiO 3 The super-cis-electric phase bismuth sodium titanate based relaxation energy storage ceramic material is prepared by sintering by a solid phase reaction method, and the chemical general formula of the super-cis-electric phase bismuth sodium titanate based relaxation energy storage ceramic material is (1-x) (0.6 Na 0.5 Bi 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 )–xSmFeO 3 Wherein x is mole fraction, x is a value range of 0.05-0.15.
The invention also discloses a preparation method of the super-cis-electric-phase sodium bismuth titanate-based relaxation energy storage ceramic material, which comprises the following steps of:
step S1: batching to analyze pure Bi 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 、Sm 2 O 3 、Fe 2 O 3 Is used as raw material and is shown as the chemical formula (1-x) (0.6 Na 0.5 Bi 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 )–xSmFeO 3 Weighing the raw materials according to the stoichiometric ratio of the system;
step S2: ball milling is carried out once, the raw materials weighed in the step S1 are placed in a nylon ball milling tank, absolute ethyl alcohol is used as a medium, zirconia balls are used as ball milling balls, then the obtained slurry is placed in an oven, and the slurry is dried at 80 ℃ to obtain massive powder;
step S3: calcining, namely mashing the block-shaped powder dried in the step S2, placing the mashed powder into a mortar for fine grinding, then placing the powder ground into fine particles into a crucible for compaction, calcining for 6 hours at the temperature of 850 ℃ at the speed of 5 ℃/min, and naturally cooling to obtain calcined powder;
step S4: secondary ball milling, namely re-milling the calcined powder obtained in the step S3, and performing ball milling and drying again according to the step S2 to obtain massive powder;
step S5: tabletting and forming, namely grinding the massive powder obtained in the step S4, adding a certain amount of PVA aqueous solution for granulating, and then placing the granulated powder into a die for compression and forming to obtain a green compact tablet;
step S6: sintering into porcelain, placing the green sheet obtained in the step S5 into a crucible, covering the crucible with the calcined powder obtained in the step S3, and sintering for two hours at 1150-1170 ℃ to obtain a porcelain-forming ceramic sheet;
step S7: and (3) manufacturing a ceramic plate electrode, polishing the ceramic plate obtained by sintering in the step (S6), and applying a gold electrode in an ion sputtering mode to be electrically tested.
Preferably, in the step S2, the mass ratio of the zirconia balls to the raw materials is 3:1, the ball milling rotating speed is 300r/min, and the ball milling time is 24 hours.
Preferably, the concentration of the PVA aqueous solution used in the step S5 is 3wt%, the granulation is completed, the powder is in a fine sand shape, the mode selected for compression molding is cold isostatic pressing, the pressure is set to 200MPa, and the dwell time is 3 minutes.
Preferably, the sintering temperature in step S6 is specifically: the temperature is increased to 500 ℃ at 3 ℃/min for 30 minutes to remove PVA, then is increased to 1150-1170 ℃ at 4 ℃/min for 2 hours, and finally is reduced to 650 ℃ at 6 ℃/min, and then is naturally cooled.
The invention has the beneficial effects that:
1. the invention can effectively overcome the defects of higher remnant polarization intensity and P-E curve bending in the traditional relaxation ferroelectric material, greatly improves the discharge energy density and energy storage efficiency of the dielectric material, and has the performance obviously superior to that of undoped 0.6Na 0.5 Bi 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 A relaxed ferroelectric material.
2. The preparation method has the advantages of simple process, easily available raw materials and high production efficiency, and is suitable for large-scale practical production and application.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation on the invention.
FIG. 1 is a graph showing the relationship between the discharge energy density and the energy storage efficiency of the super-cis-electric phase sodium bismuth titanate based relaxation energy storage ceramic prepared in example 1 and the electric field intensity;
FIG. 2 is a graph of the hysteresis loop and nonlinear fit of the super-cis-electric phase bismuth sodium titanate-based relaxation energy storage ceramic prepared in example 1 under the breakdown electric field;
FIG. 3 is a graph showing the relationship between the discharge energy density and the energy storage efficiency of the super-cis-electric phase sodium bismuth titanate based relaxation energy storage ceramic prepared in example 2 and the electric field intensity;
FIG. 4 is a graph of the hysteresis loop and nonlinear fit of the super-cis-electric phase bismuth sodium titanate-based relaxed energy storage ceramic prepared in example 2 under the breakdown electric field;
FIG. 5 is a graph showing the relationship between the dielectric constant and dielectric loss of the super-cis-electric phase sodium bismuth titanate based relaxation energy storage ceramic prepared in example 2 and the temperature and frequency;
FIG. 6 is a graph of energy storage performance versus temperature for the super-cis-electric phase sodium bismuth titanate based relaxation energy storage ceramic prepared in example 2;
FIG. 7 is a graph of energy storage performance versus frequency for the super-cis-electric phase sodium bismuth titanate based relaxation energy storage ceramic prepared in example 2;
FIG. 8 is a graph showing the relationship between the discharge energy density and the energy storage efficiency of the super-cis-electric phase sodium bismuth titanate based relaxation energy storage ceramic prepared in example 3 and the electric field intensity;
fig. 9 is a graph of the hysteresis loop and nonlinear fit of the supercis-electric phase bismuth sodium titanate-based relaxation energy storage ceramic prepared in example 3 under a breakdown electric field.
Detailed Description
Reference will now be made in detail to the present embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein the accompanying drawings are used to supplement the description of the written description so that one can intuitively and intuitively understand each technical feature and overall technical scheme of the present invention, but not to limit the scope of the present invention.
The preferred embodiment of the invention is a superparamagnetic phase bismuth sodium titanate based relaxation energy storage ceramic material which is composed of a ferroelectric material component SmFeO 3 0.6Na with relaxed ferroelectric material 0.5 Bi 0.5 TiO 3 –0.4Sr 0.7 Bi 0.2 TiO 3 The super-cis-electric phase bismuth sodium titanate based relaxation energy storage ceramic material is prepared by sintering by a solid phase reaction method, and the chemical general formula of the super-cis-electric phase bismuth sodium titanate based relaxation energy storage ceramic material is (1-x) (0.6 Na 0.5 Bi 0.5 TiO 3 –0.4Sr 0.7 Bi 0.2 TiO 3 )–xSmFeO 3 Wherein x is mole fraction, x is a value range of 0.05-0.15.
The preparation method of the super-cis-electric-phase sodium bismuth titanate-based relaxation energy storage ceramic material comprises the following steps of:
step S1: batching to analyze pure Bi 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 、Sm 2 O 3 、Fe 2 O 3 Is used as raw material and is shown as the chemical formula (1-x) (0.6 Na 0.5 Bi 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 )–xSmFeO 3 Weighing the raw materials according to the stoichiometric ratio of the system;
step S2: ball milling is carried out for one time, the raw materials weighed in the step S1 are placed in a nylon ball milling tank, absolute ethyl alcohol is used as a medium, zirconia balls are used as ball milling balls, wherein the total mass of the zirconia ball milling balls is that the total mass of mixed raw materials is 3:1, mixed ball milling is carried out for 24 hours, then the obtained slurry is placed in an oven, and the obtained slurry is dried at 80 ℃ to obtain massive powder;
step S3: calcining, namely mashing the block-shaped powder dried in the step S2, placing the mashed powder into a mortar for fine grinding, then placing the powder ground into fine particles into a crucible for compaction, calcining for 6 hours at the temperature of 850 ℃ at the speed of 5 ℃/min, and naturally cooling to obtain calcined powder;
step S4: secondary ball milling, namely re-grinding the powder calcined in the step S3, and performing ball milling and drying again according to the step S2 to obtain massive powder;
step S5: tabletting and forming, namely grinding the massive powder obtained in the step S4, adding a certain amount of PVA aqueous solution for granulating, and then placing the granulated powder into a die for compression and forming to obtain a green compact tablet;
specifically, the concentration of the PVA aqueous solution is 3wt%, the granulating is completed, the powder is in a fine sand shape, the mode selected for compression molding is cold isostatic pressing, the pressure is set to 200MPa, and the pressure maintaining time is 3 minutes;
step S6: sintering into porcelain, placing the green sheet obtained in the step S5 into a crucible, covering the crucible with the calcined powder in the step S3, and sintering for two hours at 1150-1170 ℃ to obtain a porcelain-forming ceramic sheet;
specifically, the sintering temperature is specifically: keeping the temperature at 3 ℃/min to 500 ℃ for 30 minutes to remove PVA, keeping the temperature at 4 ℃/min to 1150-1170 ℃ for 2 hours, and finally cooling to 650 ℃ at 6 ℃/min and then naturally cooling;
step S7: manufacturing a ceramic plate electrode: polishing the ceramic sheet obtained by sintering in the step S6, and applying a gold electrode by adopting an ion sputtering mode to test electrically.
The invention usesTypical 0.6Na 0.5 Bi 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 The relaxation ferroelectric ceramic material is taken as a matrix and doped with ferroelectric components SmFeO 3 Realizes the super-cis electric phase regulation and control of the matrix and utilizes SmFeO 3 Modified 0.6Na 0.5 Bi 0.5 TiO 3 –0.4Sr 0.7 Bi 0.2 TiO 3 The relaxation ferroelectric ceramic material is gradually changed from the relaxation ferroelectric phase before undoped to the super paraelectric phase along with the increase of doping amount, and the ceramic in the super paraelectric phase state has nano domains with superfine scale, is more sensitive to an electric field and faster in response, and can generate almost zero residual polarization intensity and a linear-like P-E curve.
To achieve two energy storage advantages:
1. further reducing the remnant polarization of the relaxor ferroelectric to almost zero;
2. the P-E curve of the relaxation ferroelectric bending is regulated to be similar to a linear type, and the discharge energy density and the energy storage efficiency are further improved.
The invention can effectively overcome the defects of higher remnant polarization intensity and P-E curve bending in the traditional relaxation ferroelectric material, greatly improves the discharge energy density and energy storage efficiency of the dielectric material, and has the performance obviously superior to that of undoped 0.6Na 0.5 Bi 0.5 TiO 3 –0.4Sr 0.7 Bi 0.2 TiO 3 A relaxed ferroelectric material.
The preparation method has the advantages of simple process, easily available raw materials and high production efficiency, and is suitable for large-scale practical production and application.
Furthermore, the invention proposes for the first time a linear fit and curvature calculation of the P-E curve to evaluate the energy storage performance.
Example 1
As shown in fig. 1-2, the following component expressions of the supercis electric phase sodium bismuth titanate based relaxation energy storage ceramic in this embodiment are shown: 0.95 (0.6 Na 0.5 Bi 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 )–0.05SmFeO 3 The preparation method comprises the following steps:
step S1: batching to analyze pure Bi 2 O 3 ,Na 2 CO 3 ,TiO 2 ,SrCO 3 ,Sm 2 O 3 ,Fe 2 O 3 Weighing raw materials with corresponding mass according to the stoichiometric ratio in the chemical formula;
step S2: placing the weighed raw materials in the step S1 into a nylon ball milling tank, taking absolute ethyl alcohol as a medium, and taking zirconia balls as ball milling balls, wherein the total mass of the zirconia ball milling balls is as follows: total mass of mixed raw materials = 3:1, carrying out mixed ball milling for 24 hours, and then placing the obtained slurry in an oven to be dried at 80 ℃ to obtain massive powder;
step S3: calcining, namely mashing the block-shaped powder dried in the step S2, placing the mashed powder into a mortar for fine grinding, then placing the powder ground into fine particles into a crucible for compaction, calcining for 6 hours at the temperature of 850 ℃ at the speed of 5 ℃/min, and naturally cooling to obtain calcined powder;
step S4: secondary ball milling, namely re-grinding the powder calcined in the step S3, and performing ball milling and drying again according to the step S2 to obtain massive powder;
step S5: tabletting and forming, namely grinding the massive powder obtained in the step S4, adding a certain amount of PVA aqueous solution for granulating, and then placing the granulated powder into a die for compression and forming to obtain a green compact tablet;
step S6: sintering into porcelain, placing the green sheet obtained in the step S5 into a crucible, covering the crucible with the calcined powder in the step S3, and sintering for two hours at 1150-1170 ℃ to obtain the dense and uniform-grain super-cis-electric phase bismuth sodium titanate-based relaxation energy storage ceramic; the prepared super-cis-electric phase sodium bismuth titanate-based relaxation energy storage ceramic is tested for performance at room temperature, and the results are shown in table 1. The charge and discharge energy density and the energy storage efficiency are calculated by adopting a ferroelectric hysteresis loop measured by a ferroelectric analyzer Polyk, and the calculation method comprises the following steps:
therein, W, W rec η is the charge energy density, discharge energy density and energy storage efficiency of the dielectric ceramic respectively; E. p (P) max ，P r Representing the external electric field to which the dielectric ceramic is subjected, and the maximum polarization under the external electric field and the remnant polarization after removal of the electric field, respectively.
The related electric hysteresis loop curvature value (K) is obtained by calculating and selecting the maximum value according to the fitted electric hysteresis loop, and the calculating method comprises the following steps:
K＝dθ/ds＝y″(x)/{1+[y′(x)] 2 } 3/2
the relationship between the discharge energy density and the energy storage efficiency with the electric field strength is shown in fig. 1, and the curve after fitting the electric hysteresis loop and the corresponding nonlinear curvature under the maximum applicable electric field is shown in fig. 2. 0.95 (0.6 Na 0.5 Bi 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 )–0.05SmFeO 3 The maximum breakdown field intensity of the ceramic plate of the system is 295kV/cm, and the discharge energy density is 4.7J/cm 3 The energy storage efficiency was maintained at 81% or more, the curvature of the P-E curve was 0.29, and specific energy storage properties and curvature parameters are shown in table 1.
Table 1 example 1 supercis electrical phase bismuth sodium titanate based relaxed energy storage ceramic properties
Example 2
As shown in fig. 3-7, the following component expressions of the supercis electric phase sodium bismuth titanate based relaxation energy storage ceramic in this embodiment are shown: 0.90 (0.6 Na 0.5 Bi 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 )–0.10SmFeO 3 The preparation method comprises the following steps:
to analyze pure Bi 2 O 3 ,Na 2 CO 3 ,TiO 2 ,SrCO 3 ,Sm 2 O 3 ,Fe 2 O 3 The raw materials were prepared in accordance with the stoichiometric ratio in the above chemical formula, and the rest of the procedure was as in example 1.
The experimental results are shown in table 2, wherein the change of the discharge energy storage density and the energy storage efficiency along with the electric field strength is shown in fig. 3, and the curve after fitting the hysteresis loop and the corresponding nonlinear curvature under the maximum applicable electric field is shown in fig. 4. The change of dielectric constant and dielectric loss with temperature and frequency is shown in FIG. 5, the change of energy storage performance with temperature obtained by testing at 200kV/cm is shown in FIG. 6, and the change of energy storage performance with frequency obtained by testing at 300kV/cm is shown in FIG. 7. As can be seen from the figure, 0.90 (0.6 Na 0.5 Bi 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 )–0.10SmFeO 3 The maximum breakdown field intensity of the ceramic plate of the system can reach 430kV/cm, and the discharge energy density can reach 7.2J/cm 3 The energy storage efficiency is more than 86%, the curvature of the hysteresis loop is 0.02, the quasi-linear degree is greatly enhanced, and the specific performance is shown in table 2.
Table 2 example 2 supercis electrical phase bismuth sodium titanate based relaxed energy storage ceramic properties
EXAMPLE 3,
As shown in fig. 8-9, the following component expressions of the supercis electric phase sodium bismuth titanate based relaxation energy storage ceramic in this embodiment are shown: 0.85 (0.6 Na 0.5 Bi 0.5 TiO 3 –0.4Sr 0.7 Bi 0.2 TiO 3 )–0.15SmFeO 3 The preparation method comprises the following steps:
to analyze pure Bi 2 O 3 ,Na 2 CO 3 ,TiO 2 ,SrCO 3 ,Sm 2 O 3 ,Fe 2 O 3 The raw materials were prepared in accordance with the stoichiometric ratio in the above chemical formula, and the rest of the procedure was as in example 1.
The experimental results are shown in table 3, wherein the change of discharge energy density and energy storage efficiency with the electric field strength is shown in fig. 8, and the curve after fitting the hysteresis loop and the corresponding nonlinear curvature under the maximum applicable electric field is shown in fig. 9. 0.85 (0.6 Na 0.5 Bi 0.5 TiO 3 –0.4Sr 0.7 Bi 0.2 TiO 3 )–0.15SmFeO 3 The maximum breakdown field intensity of the system ceramic plate is 322kV/cm, and the discharge energy density is 3.27J/cm 3 The energy storage efficiency is up to 92% or more, and the curvature is 6.5X10 -7 The hysteresis loop was almost straight and the specific properties are shown in table 2.
TABLE 3 example 3 Supersshun electrical phase bismuth sodium titanate based relaxed energy storage ceramic Properties
The above additional technical features can be freely combined and superimposed by a person skilled in the art without conflict.
The foregoing is only a preferred embodiment of the present invention, and all technical solutions for achieving the object of the present invention by substantially the same means are within the scope of the present invention.
Claims (5)
1. A super-cis-electric phase bismuth sodium titanate based relaxation energy storage ceramic material is characterized in that: the super paraelectric phase bismuth sodium titanate based relaxation energy storage ceramic material is composed of ferroelectric material component SmFeO 3 0.6Na with relaxed ferroelectric material 0.5 Bi 0.5 TiO 3 –0.4Sr 0.7 Bi 0.2 TiO 3 The super-cis-electric phase bismuth sodium titanate based relaxation energy storage ceramic material is prepared by sintering by a solid phase reaction method, and the chemical general formula of the super-cis-electric phase bismuth sodium titanate based relaxation energy storage ceramic material is (1-x) (0.6 Na 0.5 Bi 0.5 TiO 3 –0.4Sr 0.7 Bi 0.2 TiO 3 )–xSmFeO 3 Wherein x is mole fraction, x is a value range of 0.05-0.15.
2. A method for preparing a super-cis-electric-phase sodium bismuth titanate-based relaxation energy storage ceramic material, which comprises the steps of: the preparation method comprises the following steps:
step S1: batching to analyze pure Bi 2 O 3 、Na 2 CO 3 、TiO 2 、SrCO 3 、Sm 2 O 3 、Fe 2 O 3 Is used as raw material and is shown as the chemical formula (1-x) (0.6 Na 0.5 Bi 0.5 TiO 3 -0.4Sr 0.7 Bi 0.2 TiO 3 )–xSmFeO 3 Weighing the raw materials according to the stoichiometric ratio of the system;
step S2: ball milling is carried out once, the raw materials weighed in the step S1 are placed in a nylon ball milling tank, absolute ethyl alcohol is used as a medium, zirconia balls are used as ball milling balls, then the obtained slurry is placed in an oven, and the slurry is dried at 80 ℃ to obtain massive powder;
step S3: calcining, namely mashing the block-shaped powder dried in the step S2, placing the mashed powder into a mortar for fine grinding, then placing the powder ground into fine particles into a crucible for compaction, calcining for 6 hours at the temperature of 850 ℃ at the speed of 5 ℃/min, and naturally cooling to obtain calcined powder;
step S4: secondary ball milling, namely re-milling the calcined powder obtained in the step S3, and performing ball milling and drying again according to the step S2 to obtain massive powder;
step S5: tabletting and forming, namely grinding the massive powder obtained in the step S4, adding a certain amount of PVA aqueous solution for granulating, and then placing the granulated powder into a die for compression and forming to obtain a green compact tablet;
step S6: sintering into porcelain, placing the green sheet obtained in the step S5 into a crucible, covering the crucible with the calcined powder obtained in the step S3, and sintering for two hours at 1150-1170 ℃ to obtain a porcelain-forming ceramic sheet;
step S7: manufacturing a ceramic plate electrode: polishing the ceramic sheet obtained by sintering in the step S6, and applying a gold electrode by adopting an ion sputtering mode to test electrically.
3. The method for preparing the super-cis-electric-phase sodium bismuth titanate-based relaxation energy storage ceramic material according to claim 2, which is characterized by comprising the following steps: in the step S2, the mass ratio of the zirconia balls to the raw materials is 3:1, the ball milling rotating speed is 300r/min, and the ball milling time is 24 hours.
4. The method for preparing the super-cis-electric-phase sodium bismuth titanate-based relaxation energy storage ceramic material according to claim 2, which is characterized by comprising the following steps: the concentration of PVA aqueous solution used in the step S5 is 3wt%, the pelletization is completed, the powder is in a fine sand shape, the mode selected for compression molding is cold isostatic pressing, the pressure is set to 200MPa, and the pressure maintaining time is 3 minutes.
5. The method for preparing the super-cis-electric-phase sodium bismuth titanate-based relaxation energy storage ceramic material according to claim 2, which is characterized by comprising the following steps: the sintering temperature in step S6 is specifically: the temperature is increased to 500 ℃ at 3 ℃/min for 30 minutes to remove PVA, then is increased to 1150-1170 ℃ at 4 ℃/min for 2 hours, and finally is reduced to 650 ℃ at 6 ℃/min, and then is naturally cooled.
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