CN115724660A - Barium titanate/calcium ortho-dititanate composite ceramic and preparation method and application thereof - Google Patents
Barium titanate/calcium ortho-dititanate composite ceramic and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011575 calcium Substances 0.000 title abstract description 61
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title abstract description 12
- 229910002113 barium titanate Inorganic materials 0.000 title abstract description 5
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title abstract description 5
- 238000004146 energy storage Methods 0.000 claims abstract description 22
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 14
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- 229910052719 titanium Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
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- 230000010287 polarization Effects 0.000 description 6
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- -1 batteries Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 description 1
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y02E60/50—Fuel cells
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Abstract
The invention belongs to the technical field of piezoelectric materials, and particularly relates to barium titanate/calcium ortho-dititanate composite ceramic and a preparation method and application thereof. The invention provides BaTiO 3 /Ca 3 Ti 2 O 7 Composite ceramic comprising Ca 3 Ti 2 O 7 And BaTiO 3 (ii) a The Ca 3 Ti 2 O 7 And BaTiO 3 In a molar ratio of 1 to 3:7 to 9. According to the invention, through the components and the component proportion of the composite ceramic, the mechanical stress generated by the deformation of the composite ceramic under an externally-applied driving electric field is effectively regulated and controlled, so that the deformation of the composite ceramic is reduced, and the energy storage efficiency and the fatigue resistance of the composite ceramic are improved.
Description
Technical Field
The invention belongs to the technical field of piezoelectric materials, and particularly relates to barium titanate/calcium ortho-dititanate composite ceramic and a preparation method and application thereof.
Background
Currently, research in energy storage technology is mainly focused on dielectric capacitors, electrochemical capacitors, batteries, and solid oxide fuel cells. Dielectric capacitors have a lower energy storage density but a higher power density than several other energy storage technologies. If the energy storage density of the dielectric ceramic capacitor is increased, it is advantageous for the miniaturization and weight reduction of electronic components. Although increasing the applied electric field strength can increase the energy storage density of the ceramic capacitor, the ceramic capacitor has a larger volume change under a high electric field, which inevitably leads to loss of the device, and the energy storage performance is significantly reduced.
However, at present, there is no ideal material which can be used for energy storage and cannot deform under an electric field, and most of conventional ferroelectric ceramic materials exhibit a positive piezoelectric effect, that is, when a polarization direction is the same as an external electric field direction, the material will deform in a tensile manner in the external electric field direction, and a negative piezoelectric effect is opposite to the external electric field direction. At present, only four CuInP negative-pressure electric materials reported at home and abroad are available 2 S 6 PVDF, BTAs and Ca 3 Ti 2 O 7 The first three of them (CuInP) 2 S 6 PVDF and BTAs) are all organic materials, only Ca 3 Ti 2 O 7 Is an inorganic material. However, whether the material is a positive piezoelectric material or a negative piezoelectric material, the material cannot be prevented from generating large deformation in an electric field, so that the energy storage efficiency is reduced (generally, the energy storage efficiency is 40-50%).
Disclosure of Invention
In view of the above, the present invention aims to provide a barium titanate/calcium n-dititanate composite ceramic, and a preparation method and applications thereof. The BaTiO provided by the invention 3 /Ca 3 Ti 2 O 7 The composite ceramic has low deformation in an electric field and high energy storage efficiency.
In order to solve the above problems, the present invention provides a BaTiO 3 /Ca 3 Ti 2 O 7 Composite ceramic comprising Ca 3 Ti 2 O 7 And BaTiO 3 (ii) a The Ca 3 Ti 2 O 7 And BaTiO 3 In a molar ratio of 1 to 3:7 to 9.
The invention also provides the BaTiO 3 /Ca 3 Ti 2 O 7 The preparation method of the composite ceramic comprises the following steps:
mixing Ca 3 Ti 2 O 7 Powder and BaTiO 3 Powder ofSequentially mixing, pressing and sintering to obtain the BaTiO 3 /Ca 3 Ti 2 O 7 Composite ceramics;
the Ca 3 Ti 2 O 7 Powder and BaTiO 3 The molar ratio of the powder is 1-3: 7 to 9.
Preferably, the Ca 3 Ti 2 O 7 The grain diameter of the powder is 74-150 mu m; the BaTiO 3 The particle size of the powder is 74-150 μm.
Preferably, the mixing mode is wet grinding, the rotation speed of the wet grinding is 200-400 rpm, and the time is 8-12 h.
Preferably, the pressure of the pressing is 20-40 MPa, and the time is 10-20 min.
Preferably, the sintering temperature is 1300-1500 ℃, and the time is 5-15 h.
Preferably, the rate of temperature rise to the sintering temperature is 3 to 7 ℃/min.
The invention also provides the BaTiO 3 /Ca 3 Ti 2 O 7 Use of a composite ceramic in a dielectric energy storage device.
Preferably, the dielectric energy storage device comprises a dielectric capacitor, a piezoelectric displacement actuator or a micro-ceramic actuator.
The invention provides BaTiO 3 /Ca 3 Ti 2 O 7 Composite ceramics of Ca 3 Ti 2 O 7 And BaTiO 3 The Ca 3 Ti 2 O 7 And BaTiO 3 In a molar ratio of 1 to 3:7 to 9. According to the invention, through the components and the component proportion of the composite ceramic, the mechanical stress generated by the deformation of the composite ceramic under an externally-applied driving electric field is effectively regulated and controlled, so that the deformation of the composite ceramic is reduced, and the energy storage efficiency and the fatigue resistance of the composite ceramic are improved.
Drawings
FIG. 1 is a graph of X-ray diffraction refined fits of BT-0.1CT, BT-0.2CT, and BT-0.3CT composite ceramics prepared in examples 1-3;
FIG. 2 is a graph showing ferroelectric property test of BT-0.1CT, BT-0.2CT and BT-0.3CT prepared in examples 1 to 3;
FIG. 3 is a graph showing the variation of the displacement of BT-0.1CT, BT-0.2CT and BT-0.3CT composite ceramics prepared in examples 1 to 3 with an external electric field;
FIG. 4 is a hysteresis chart of BT-0.1CT, BT-0.2CT, and BT-0.3CT composite ceramics prepared in examples 1 to 3 under the action of an applied electric field.
Detailed Description
The invention provides BaTiO 3 /Ca 3 Ti 2 O 7 Composite ceramic comprising Ca 3 Ti 2 O 7 And BaTiO 3 The Ca 3 Ti 2 O 7 And BaTiO 3 In a molar ratio of 1 to 3:7 to 9.
In the present invention, the Ca 3 Ti 2 O 7 And BaTiO 3 In a molar ratio of 1 to 3:7 to 9, preferably 1.
In the present invention, the Ca 3 Ti 2 O 7 The preparation method preferably comprises the following steps:
mixing a calcium source and a titanium source, and then carrying out first sintering to obtain a first sintering material;
pressing the first sintering material, and then performing second sintering to obtain Ca 3 Ti 2 O 7 And (3) powder.
According to the invention, a calcium source and a titanium source are mixed and then subjected to first sintering to obtain a first sintering material.
In the present invention, the calcium source preferably comprises calcium carbonate. In the present invention, the titanium source preferably includes titanium dioxide. In the present invention, the purity of the calcium source and the titanium source is independently preferably 99.99%. In the present invention, the molar ratio of the calcium element in the calcium source to the titanium element in the titanium source is preferably 3.
In the present invention, the mixing means is preferably wet milling, and the medium for wet milling is preferably alcohol. In the present invention, the rotation speed of the wet milling is preferably 200 to 400rpm, more preferably 300rpm, and the time is preferably 8 to 12 hours, more preferably 10 hours.
In the present invention, after the wet milling, it is preferable to further dry the ball-milled material. In the present invention, the drying is not particularly limited, and the alcohol may be removed by a procedure well known to those skilled in the art.
In the present invention, the temperature of the first sintering is preferably 900 to 1100 ℃, more preferably 1000 ℃, and the time is preferably 11 to 13 hours, more preferably 12 hours.
After the first sintering material is obtained, the first sintering material is pressed and then subjected to second sintering to obtain Ca 3 Ti 2 O 7 。
In the present invention, the pressure of the pressing is preferably 20MPa, and the time is preferably 15min. In the present invention, the pressing is preferably performed by pressing the first sintered material into a disc having a diameter of about 14mm and a thickness of 0.15 to 0.3 mm. In the present invention, the temperature of the second sintering is preferably 1400 to 1500 ℃, more preferably 1450 ℃, and the time is preferably 46 to 50 hours, more preferably 48 hours. In the present invention, the second sintering is preferably performed in an air atmosphere.
In the present invention, after the second sintering, it is preferable to further include cooling the second sintered material. In the present invention, the cooling is preferably to room temperature. The cooling is not particularly limited in the present invention, and the cooling may be carried out in a furnace to room temperature.
In the present invention, the BaTiO 3 A method of preparing a powder comprising the steps of:
mixing a barium source and a titanium source, and then carrying out first sintering to obtain a first sintering material;
pressing the first sintering material, and then performing second sintering to obtain BaTiO 3 And (3) powder.
According to the invention, a calcium source and a titanium source are mixed and then subjected to first sintering to obtain a first sintering material.
In the present invention, the barium source preferably comprises barium carbonate and the titanium source preferably comprises titanium dioxide. The purity of the calcium carbonate and titanium dioxide is independently preferably 99.99%. In the present invention, the molar ratio of the barium element in the barium source to the titanium element in the titanium source is preferably 1.
In the present invention, the mixing manner and parameters of the barium source and the titanium source are preferably mixed with the calcium source and the titanium source, and are not described herein again.
In the present invention, the temperature of the first sintering of the barium source and the titanium source is preferably 900 to 1100 ℃, more preferably 1000 ℃, and the time is preferably 11 to 13 hours, more preferably 12 hours.
In the present invention, the pressure of pressing the first sintered material is preferably 15 to 30MPa, more preferably 20MPa, and the time is preferably 10 to 20min, more preferably 15min. In the present invention, the pressing is preferably performed by pressing the first sintered material into a disc having a diameter of about 14mm and a thickness of 0.15 to 0.3 mm.
After the first sintering material is obtained, the first sintering material is pressed and then subjected to second sintering to obtain BaTiO 3 And (3) powder.
In the present invention, the temperature of the second sintering is preferably 1100 to 1300 ℃, more preferably 1200 ℃, and the time is preferably 46 to 50 hours, more preferably 48 hours.
In the present invention, after the second sintering, it is preferable to further include cooling the second sintered material. In the present invention, the cooling is preferably to room temperature. The cooling is not particularly limited in the present invention, and the cooling may be carried out in a furnace to room temperature.
The invention also provides the BaTiO 3 /Ca 3 Ti 2 O 7 The preparation method of the composite ceramic comprises the following steps:
adding Ca 3 Ti 2 O 7 Powder and BaTiO 3 Sequentially mixing, pressing and sintering the powder to obtain the BaTiO 3 /Ca 3 Ti 2 O 7 Composite ceramics.
In the present invention, the Ca 3 Ti 2 O 7 Powder and BaTiO 3 The molar ratio of the powder is preferably 1 to 3. In the present invention, the Ca 3 Ti 2 O 7 The particle size of the powder is preferably 74 to 150 μm, more preferably 125 μm, and the BaTiO 3 The particle size of the powder is preferably 74 to 150. Mu.m, more preferably 125. Mu.m. In the inventionIn case of Ca 3 Ti 2 O 7 Powder and BaTiO 3 The particle size of the powder is not within the above range, and before mixing, it is preferable to further comprise grinding the above materials to the above particle size. The present invention is not particularly limited to the grinding, and the material may be ground to the above-mentioned particle size range by a procedure well known to those skilled in the art.
In the present invention, the mixing mode is preferably wet milling, the medium for the wet milling is preferably alcohol, the rotation speed of the wet milling is preferably 200 to 400rpm, more preferably 300rpm, and the time for the wet milling is preferably 9 to 12 hours, more preferably 10 to 11 hours.
In the present invention, the pressure of the pressing is preferably 20 to 40MPa, more preferably 30MPa, and the time is preferably 10 to 20min, more preferably 15min. In the present invention, the pressing is preferably performed by pressing the mixed material obtained by mixing into a disk having a diameter of about 14mm and a thickness of 0.15 to 0.3 mm.
In the present invention, the sintering temperature is preferably 1300 to 1500 ℃, more preferably 1400 ℃, and the time is preferably 5 to 15 hours, more preferably 10 hours. In the present invention, the rate of temperature rise to the sintering temperature is preferably 3 to 7 ℃/min, more preferably 5 ℃/min.
In the present invention, after the sintering, it is preferable to further include cooling the sintered material. In the present invention, the cooling is preferably to room temperature. The cooling is not particularly limited in the present invention, and the cooling may be carried out in a furnace to room temperature.
The invention also provides the BaTiO 3 /Ca 3 Ti 2 O 7 Use of a composite ceramic in a dielectric energy storage device.
In the present invention, the dielectric energy storage device preferably comprises a dielectric capacitor, a piezoelectric displacement actuator or a micro-ceramic actuator.
In order to further illustrate the present invention, the following embodiments are provided to describe the technical solutions of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing CaCO 3 (purity 99.99%)、TiO 2 (purity: 99.99%) were mixed in a molar ratio of 3,
placing in an agate jar, adding 15mL of alcohol, placing the obtained mixture in a ball mill for grinding for 10h,
after the ball milling is finished, putting the mixture into a drying box to dry alcohol to obtain a mixed material;
placing the mixed material into a crucible, placing the crucible into a muffle furnace, and performing first sintering for 12 hours at the temperature of 1000 ℃ in the air atmosphere to obtain a first sintered material;
preparing the first sintering material into a wafer with the diameter of 14mm and the thickness of 0.15-0.3 mm by using a single-shaft pressing die, sintering the wafer in air at 1400 ℃ for 48 hours, and cooling the wafer to room temperature along with a furnace to obtain Ca 3 Ti 2 O 7 。
Mixing BaCO 3 (purity: 99.99%), tiO 2 (purity is 99.99%) are mixed according to a molar ratio of 1, placed in an agate pot, 15mL of alcohol is added, the obtained mixture is placed in a ball mill for grinding for 10 hours, after the ball milling is finished, the agate pot is taken out, and placed in a drying oven for drying the alcohol, so that a mixed material is obtained;
placing the mixed material into a crucible, placing the crucible into a muffle furnace, and performing first sintering for 12 hours at the temperature of 1000 ℃ in the air atmosphere to obtain a first sintered material;
preparing the sintered material into a wafer with the diameter of 14mm and the thickness of 0.15-0.3 mm by using a single-shaft pressing die, sintering the wafer in air at 1200 ℃ for 24 hours, and cooling the wafer to room temperature along with a furnace to obtain BaTiO 3 。
Adding Ca 3 Ti 2 O 7 And BaTiO 3 Grinding in agate mortar to obtain Ca 3 Ti 2 O 7 And BaTiO 3 Powder of (2) BaTiO 3 、Ca 3 Ti 2 O 7 According to the molar ratio of 9:1, mixing, placing in an agate jar, adding 15mL of alcohol, placing the obtained mixture in a ball mill, grinding for 10 hours, taking out the agate jar after the ball milling is finished, placing in a drying oven, and drying the alcohol to obtain a mixed material;
the sintered material is made into a material with the diameter of 14mm by using a single-axis pressing die,A wafer with the thickness of 0.15-0.3 mm is sintered in air at 1300 ℃ for 12h, and then is cooled to room temperature along with a furnace to obtain the BaTiO 3 /Ca 3 Ti 2 O 7 Composite ceramic, baTiO prepared in example 1 3 /Ca 3 Ti 2 O 7 The composite ceramic is named as BT-0.1CT.
Example 2
The only difference from example 1 is that the BaTiO compound 3 、Ca 3 Ti 2 O 7 In a molar ratio of 8:2, named as BT-0.2CT.
Example 3
The only difference from example 1 is that the BaTiO compound 3 、Ca 3 Ti 2 O 7 In a molar ratio of 7:3, named as BT-0.3CT.
Performance testing
(1) X-ray diffraction measurement
The BT-0.1CT, BT-0.2CT and BT-0.3CT composite ceramics prepared in examples 1 to 3 were measured by X-ray diffraction using an X-ray diffractometer of D8 Advance model manufactured by Bruker, germany, and the tetragonal phase space group P4mm and the orthorhombic phase space group Ccm2 were selected 1 The test data were subjected to Rieveld polyphase refinement fitting, the results of which are shown in figure 1. Wherein FIGS. 1 (a) - (c) are the results of multiphase refinement fitting of BT-0.1CT, BT-0.2CT and BT-0.3CT, respectively, and it can be seen from FIG. 1 that BT-0.1CT, BT-0.2CT and BT-0.3CT all contain BaTiO 3 And Ca 3 Ti 2 O 7 Two phase structures prove that the invention successfully prepares the positive piezoelectric material BaTiO 3 With negative voltage electric material Ca 3 Ti 2 O 7 The composite ceramic of (1).
(2) Ferroelectric property test
The ferroelectric properties of BT-0.1CT, BT-0.2CT and BT-0.3CT prepared in examples 1 to 3 were tested, and the test method was: the loop graphs of the polarization intensity and polarization current of BT-0.1CT, BT-0.2CT and BT-0.3CT under an applied electric field with the frequency of 100Hz are measured at room temperature, the results are shown in FIG. 2, and the results are shown in FIG. 2, wherein Ca is the negative voltage material 3 Ti 2 O 7 With positive piezoelectric material BaTiO 3 The composite ceramic material has ironAnd (4) electrical property. And with the negative voltage material Ca 3 Ti 2 O 7 The proportion is increased, the electric hysteresis loop is gradually slender, the energy storage efficiency is obviously improved, and the energy storage efficiency is improved to 74.95 percent from the original 48.07 percent.
(3) Piezoelectric performance test
The BT-0.1CT, BT-0.2CT and BT-0.3CT composite ceramics prepared in examples 1 to 3 were subjected to a piezoelectric property test. The test method comprises the following steps: and measuring the curve graphs of the displacements of BT-0.1CT, BT-0.2CT and BT-0.3CT along with the change of the external electric field under the external electric field with the frequency of 0.1Hz by using a TF2000 ferroelectric analyzer at room temperature. The test results are shown in fig. 3, and as shown in fig. 3, all ceramic samples showed an "m" type displacement-electric field curve, i.e., as the electric field increases, the displacement of the sample along the direction of the electric field increases. But with negative piezoelectric material Ca 3 Ti 2 O 7 The proportion of the composite ceramic sample is increased, the displacement of the sample along with an electric field is gradually reduced, and the sample tends not to generate displacement. This shows that the positive piezoelectric material BaTiO prepared in the invention 3 With negative voltage material Ca 3 Ti 2 O 7 The composite ceramic can effectively regulate and control the deformation of the material under the action of an electric field.
The BT-0.1CT, BT-0.2CT and BT-0.3CT composite ceramic ceramics prepared in examples 1 to 3 were subjected to a piezoelectric property test. At room temperature, a TF2000 ferroelectric analyzer is used for measuring BT-0.1CT, BT-0.2CT and BT-0.3CT circulation 10 under an applied electric field with the frequency of 0.1Hz 5 The polarization intensity after that changes. The results are shown in FIG. 4, in which graphs (a) - (c) are respectively BT-0.1CT, BT-0.2CT and BT-0.3CT under the action of 30kV/cm applied electric field for 10 cycles at room temperature 5 The next hysteresis loop diagram and the corresponding polarization current diagram. As can be seen from fig. 4: with negative voltage electric material Ca 3 Ti 2 O 7 The proportion of the material in the composite ceramic sample is increased, and the change of the hysteresis loop and the polarization current of the material under the circulation action of an external electric field is gradually reduced, which proves that the positive piezoelectric material BaTiO prepared in the invention 3 With negative voltage material Ca 3 Ti 2 O 7 The composite ceramic can effectively enhance the fatigue durability of the material.
FIG. 4 (d) shows BT-0.Graphs of the energy density and efficiency at room temperature of 30kV/cm for 1CT, BT-0.2CT and BT-0.3CT as a function of the number of cycles, as shown in FIG. 4 (d), along with Ca, which is a negative voltage material 3 Ti 2 O 7 The proportion of the composite ceramic sample is increased, and the BT-0.3CT sample is subjected to the circulation action of an external electric field 10 5 The energy storage density is basically unchanged after the next time, and the energy storage efficiency is reduced by less than 8 percent, which shows that the BaTiO prepared by the invention 3 /Ca 3 Ti 2 O 7 The composite ceramic also shows excellent fatigue resistance.
According to the embodiment, the composite material prepared by combining the negative piezoelectric material and the positive piezoelectric material can effectively regulate and control the strain response of the material under the drive of an external electric field, and the mechanical stress generated by the deformation of the prepared electronic element under the electric field can be reduced or even approaches to zero by regulating the proportion of the two materials, so that the fatigue durability of the device is greatly improved, and the service life of the device can be effectively prolonged.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. BaTiO 3 /Ca 3 Ti 2 O 7 The composite ceramic is characterized by comprising Ca 3 Ti 2 O 7 And BaTiO 3 ；
The Ca 3 Ti 2 O 7 And BaTiO 3 In a molar ratio of 1 to 3:7 to 9.
2. BaTiO of claim 1 3 /Ca 3 Ti 2 O 7 The preparation method of the composite ceramic is characterized by comprising the following steps:
adding Ca 3 Ti 2 O 7 Powder and BaTiO 3 Sequentially mixing, pressing and sintering the powder to obtain the BaTiO 3 /Ca 3 Ti 2 O 7 Composite ceramics;
the Ca 3 Ti 2 O 7 Powder and BaTiO 3 The molar ratio of the powder is 1-3: 7 to 9.
3. The method according to claim 2, wherein the Ca is 3 Ti 2 O 7 The grain diameter of the powder is 74-150 mu m; the BaTiO 3 The particle size of the powder is 74-150 μm.
4. The method according to claim 2 or 3, wherein the mixing is performed by wet milling at a rotation speed of 200 to 400rpm for 8 to 12 hours.
5. The method according to claim 2 or 3, wherein the pressing is performed at a pressure of 20 to 40MPa for a period of 10 to 20min.
6. The method according to claim 2 or 3, wherein the sintering temperature is 1300-1500 ℃ and the sintering time is 5-15 h.
7. The production method according to claim 6, wherein the rate of temperature rise to the sintering temperature is 3 to 7 ℃/min.
8. BaTiO of claim 1 3 /Ca 3 Ti 2 O 7 Use of a composite ceramic in a dielectric energy storage device.
9. The use of claim 8, wherein the dielectric energy storage device comprises a dielectric capacitor, a piezoelectric displacement actuator or a micro-ceramic actuator.
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