CN117285354A - Silver niobate-based relaxation type ternary solid solution ceramic material with high energy storage characteristic and preparation method thereof - Google Patents
Silver niobate-based relaxation type ternary solid solution ceramic material with high energy storage characteristic and preparation method thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 107
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 53
- 239000004332 silver Substances 0.000 title claims abstract description 53
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 52
- 239000006104 solid solution Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000015556 catabolic process Effects 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 53
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 52
- 239000000919 ceramic Substances 0.000 claims description 47
- 238000000498 ball milling Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 14
- 229920003023 plastic Polymers 0.000 claims description 13
- 239000004033 plastic Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 5
- 230000005684 electric field Effects 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001923 silver oxide Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 239000002612 dispersion medium Substances 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000012071 phase Substances 0.000 description 11
- 230000010287 polarization Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 235000015895 biscuits Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005404 monopole Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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Abstract
The invention relates to a silver niobate based relaxation type ternary solid solution ceramic material with high energy storage property and a preparation method thereof, belonging to the field of functional materials. The silver niobate-based relaxation type ternary solid solution ceramic material with high energy storage property comprises the following chemical components: (1-x) (0.7 AgNbO) 3 ‑0.3NaNbO 3 )‑x(Sr 0.7 Bi 0.2 )TiO 3 Wherein x is more than or equal to 0 and less than or equal to 0.25. The novel leadless dielectric ceramic material of the invention has excellent energy storage property by introducing antiferroelectric component NaNbO 3 And a relaxation component (Sr) 0.7 Bi 0.2 )TiO 3 The ternary solid solution silver niobate-based ceramic material with greatly improved breakdown field strength and energy storage density is obtained, and has application prospect in pulse power capacitors.
Description
Technical Field
The invention relates to a silver niobate based relaxation type ternary solid solution ceramic material with high energy storage property and a preparation method thereof, belonging to the field of functional materials.
Background
The dielectric ceramic capacitor has excellent power density and ultra-fast charge and discharge rate, and has wide application prospect in the energy storage field. At present, commercial high-energy-storage ceramic dielectric materials mainly comprise lead-containing antiferroelectric compounds, but lead-based materials bring great harm to ecological environment and human health, so that the development of lead-free dielectric materials is a problem to be solved urgently. Silver niobate has a large polarization intensity (40. Mu.C/cm) 2 ) Is a popular candidate material for high energy storage applications, but has a remnant polarization strength (4. Mu.C/cm) 2 ) And the forward turning electric field is lower, so that the energy storage density and the energy storage efficiency are lower.
In recent years, a great deal of work has been done to develop means for improving the energy storage density and energy storage efficiency of silver niobate-based ceramics in the following main modes: stability of the antiferroelectric phase is enhanced by incorporating ions with an ionic radius smaller than that of silver ions at the a-site of the perovskite structure (ref: energy Storage mate, 2021, 34:417-426); doping ions having a lower polarization rate than niobium ions at the B site to reduce the remnant polarization (reference: nat. Commun.,2020,11 (1): 4824); incorporation of small radius ions and low polarizability ions at the a and B sites, respectively, achieves enhanced stability of the antiferroelectric phase and reduced remnant polarization (ref: ceram. Int.,2023,49 (11): 18143-18152). However, the current silver niobate-based energy storage ceramic is difficult to induce disordered local structures and polar nano micro-domains, so that the obtained antiferroelectric hysteresis loops are square and straight and have large hysteresis, and the cooperative improvement of energy storage density and energy storage efficiency is difficult to realize.
Disclosure of Invention
Based on the background, the invention provides a silver niobate-based relaxation type ternary solid solution ceramic material with high energy storage property and a preparation method thereof. The novel leadless dielectric ceramic material of the invention has excellent energy storage property by introducing antiferroelectric component NaNbO 3 And a relaxation component (Sr) 0.7 Bi 0.2 )TiO 3 The ternary solid solution silver niobate-based ceramic material with greatly improved breakdown field strength and energy storage density is obtained, and has application prospect in pulse power capacitors.
In a first aspect, the present invention providesA silver niobate based relaxation type ternary solid solution ceramic material with high energy storage property. The silver niobate based relaxation type ternary solid solution ceramic material with high energy storage property comprises the following chemical components: (1-x) (0.7 AgNbO) 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Wherein x is more than or equal to 0 and less than or equal to 0.25.
According to the invention, the silver niobate-based ceramic material with complex material composition is designed through multi-system solid dissolution, so that the lattice disorder degree of the material is increased, the atomic configuration entropy is increased, the ferroelectric long-range order is broken, and the silver niobate-based relaxation ceramic with narrow oblique hysteresis loop is obtained. The advantages of each solid solution system are combined, so that the cooperative improvement of the energy storage density and the energy storage efficiency is realized, and the characteristics of strong breakdown field, high energy storage density and the like are realized.
Preferably, 0.18.ltoreq.x.ltoreq.0.25.
Preferably, the breakdown electric field of the silver niobate-based relaxation type ternary solid solution ceramic material with high energy storage property is 444-489 kV/cm; the recyclable energy storage density is 5.55-6.69J/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The energy storage efficiency is 53.7-76.9%.
In a second aspect, the invention provides a preparation method of a silver niobate-based relaxation type ternary solid solution ceramic material with high energy storage property. The preparation method comprises the following steps:
(1) According to the stoichiometric ratio (1-x) (0.7 AgNbO) 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Weighing silver oxide powder, niobium pentoxide powder, titanium dioxide powder, sodium carbonate powder, bismuth oxide powder and strontium titanate powder as raw material powder, mixing, calcining and finely grinding to obtain synthetic powder;
(2) Mixing the obtained synthetic powder with a binder, granulating, aging, sieving and forming to obtain a ceramic green body;
(3) And (3) performing plastic removal and sintering on the obtained ceramic green body to obtain the silver niobate-based relaxation type ternary solid solution ceramic material with high energy storage property.
Preferably, in the step (1), the mixing mode is ball milling mixing; preferably, absolute ethyl alcohol is used as a dispersion medium, the ball milling rotating speed is 230-250 rpm, and the ball milling time is 4-6 hours; more preferably, the ball milling media are zirconia balls and/or zirconia columns.
Preferably, in the step (1), the calcining atmosphere is oxygen atmosphere, the calcining temperature is 850-870 ℃, and the calcining time is 2-4 hours.
Preferably, in the step (2), the binder is a polyvinyl alcohol aqueous solution with the concentration of 5-7wt%; the addition amount of the binder is 6-7wt% of the mass of the synthesized powder; the sieved screen mesh is 20-80 meshes.
Preferably, in the step (3), the temperature of the plastic discharge is 700-800 ℃ and the time is 2-3 hours.
Preferably, in the step (3), the sintering temperature is 980-1060 ℃ and the sintering time is 2-3 hours; the temperature rising rate of the sintering is not higher than 2 ℃/min. Preferably, the temperature rising rate of the sintering is 1-2 ℃/min.
Drawings
Other features, objects and advantages of the present invention will become more apparent from the detailed description of non-limiting embodiments, which proceeds with reference to the accompanying drawings.
FIG. 1 is an X-ray diffraction pattern of examples 1, 2, 3,4, 1, 2, 3 of the present invention;
FIG. 2 is a surface micro-topography of example 1 of the present invention;
FIG. 3 is a surface micro topography of example 2 of the present invention;
FIG. 4 is a surface microtopography of example 3 of the present invention;
FIG. 5 is a surface micro-topography of comparative example 1 of the present invention;
FIG. 6 is a surface microtopography of comparative example 2 of the present invention;
FIG. 7 is a graph showing the change in dielectric constant with temperature for example 2 of the present invention;
FIG. 8 is a graph showing the change in dielectric constant with temperature of comparative example 3 of the present invention;
FIG. 9 is a monopolar hysteresis loop chart of embodiment 1 of the present invention;
FIG. 10 is a monopolar hysteresis loop chart of embodiment 2 of the present invention;
FIG. 11 is a monopolar hysteresis loop chart of embodiment 3 of the present invention;
FIG. 12 is a monopolar hysteresis loop chart of embodiment 4 of the present invention;
FIG. 13 is a monopolar hysteresis loop graph of comparative example 1 of the present invention;
FIG. 14 is a monopolar hysteresis loop graph of comparative example 2 of the present invention;
FIG. 15 is a monopolar hysteresis loop graph of comparative example 3 of the present invention;
fig. 16 is a graph of energy storage density and energy storage efficiency as a function of x for a silver niobate-based relaxed ternary solid solution ceramic material of the present invention.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
The silver niobate based relaxation type ternary solid solution ceramic material with high energy storage characteristic (also called as silver niobate based relaxation type energy storage ceramic material or silver niobate based relaxation type energy storage ceramic material for energy storage) has the chemical composition of (1-x) (0.7 AgNbO) 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Wherein x=0 to 0.25. When x is higher than 0.25, saturation polarization is reduced, and energy storage density is lowered.
The silver niobate based relaxation type ternary solid solution ceramic material with high energy storage property is prepared by introducing NaNbO 3 To increase the solid solubility of silver niobate, to increase the breakdown field strength, and to introduce a relaxation component (Sr) 0.7 Bi 0.2 )TiO 3 To induce disordered local structure and polar nanometer micro-area, reduce residual polarization intensity, improve breakdown field intensity, and improve energy storage density and energy storage efficiency. That is, the present invention is realized by introducing NaNbO 3 To increase AgNbO 3 By introducing a relaxation component (Sr) 0.7 Bi 0.2 )TiO 3 The configuration entropy of the material system is further increased, the relaxation characteristic of the material system is induced, and excellent energy storage performance is obtained. The method provides a new idea for the design of a novel lead-free energy storage material system.
NaNbO 3 Has antiferroelectric property, straight electric hysteresis loop and no relaxation property, and only introduces antiferroelectric component NaNbO 3 The ferrielectric characteristic of the material system can not be changed, the hysteresis is still larger, and the energy storage efficiency is lower. (Sr) 0.7 Bi 0.2 )TiO 3 Has relaxation properties, and introduces only a relaxation component (Sr 0.7 Bi 0.2 )TiO 3 Time (Sr) 0.7 Bi 0.2 )TiO 3 Cannot be combined with AgNbO 3 And (3) carrying out large-proportion solid solution.
Preferably 0.18.ltoreq.x.ltoreq.0.25. The phenomenon of narrow inclined electric hysteresis loop can be observed in the component range, and relatively higher breakdown electric field intensity, effective energy storage density and energy storage efficiency are obtained.
The silver niobate based relaxation type energy storage ceramic material can be prepared by adopting a solid phase reaction method under an oxygen atmosphere. For example, the steps of batching, mixing, briquetting, synthesizing, crushing, fine grinding, forming, plastic discharging, sintering and the like can be included. The following illustrates the preparation method of the silver niobate-based relaxation type energy storage ceramic material.
Step 1, synthesis is performed by a solid phase method. According to the stoichiometric ratio (1-x) (0.7 AgNbO) 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Weighing silver oxide powder, niobium pentoxide powder, titanium dioxide powder, sodium carbonate powder, bismuth oxide powder and strontium titanate powder as raw material powder, mixing, calcining and finely grinding to obtain synthetic powder.
The purity of the raw material powder is more than 99 percent. As an example, silver oxide powder, niobium oxide powder, titanium dioxide powder, sodium carbonate powder, bismuth oxide powder and strontium titanate powder having a purity of more than 99% were selected as raw materials and weighed in accordance with a molar ratio of Ag: na: nb: sr: bi: ti= (0.7-0.7 x): (0.3-0.3 x): (1-x): 0.7x:0.2x: x.
The raw material powders can be uniformly mixed by adopting a ball milling method. The ball milling parameters include: absolute ethyl alcohol is used as a dispersion medium, the ball milling rotating speed is 230-250 rpm, and the ball milling time is 4-6 h. The ball milling media may be zirconia balls and/or zirconia columns. For example, zirconia balls having a diameter of 6mm and a diameter of 10mm are used as the ball milling medium. The mass ratio of zirconia balls with the diameter of 6mm and the diameter of 10mm can be 3:2. the mass ratio of the raw material powder, the ball milling medium and the absolute ethyl alcohol in the ball milling process can be changed according to the requirement. For example, raw material powder: ball milling medium: the mass ratio of the absolute ethyl alcohol can be 1:4.5:1.8. the ball milling (mixing) time may be 4 hours. Drying and sieving can be performed after ball milling. And compacting the sieved powder into a block at a pressure of 1-4 MPa, for example 3 MPa.
The calcination temperature (synthesis temperature) may be 850 to 870 ℃. As an example, the powder mass to be synthesized is placed in a closed container (e.g., a closed alumina crucible) to perform the synthesis, thereby reducing volatilization of Na component and Bi component and slag pollution. Calcination is carried out, for example, in a muffle furnace with an oxygen atmosphere. Preferably, the synthesis reaction is allowed to occur sufficiently by increasing the temperature to the synthesis temperature at a rate of not more than 2 ℃/min. The atmosphere of closed calcination is oxygen atmosphere. As an example, the calcination temperature is 870 ℃ and the calcination time is 4h.
The calcined product can be cooled to room temperature along with a furnace. The synthesized ceramic powder can be crushed and sieved (for example, 20-80 meshes), so that the subsequent process efficiency is improved, and the preparation time is saved.
And step 2, molding the obtained synthetic powder to obtain a ceramic biscuit (also called ceramic green body). For example, the synthetic powder is finely ground, granulated, aged and compression molded to obtain a ceramic green body.
The synthetic powder may be finely ground prior to forming. The fine milling process may be wet ball milling. The ball milling media may be zirconia balls and/or zirconia columns. For example, the ball milling media are zirconia columns and zirconia balls. Zirconia balls having diameters of 1mm, 6mm, 10mm may be used. Zirconia column, zirconia balls with the diameter of 6mm and zirconia balls with the diameter of 10mm with the mass ratio of 1-1.5: 1 to 1.5:1 to 1.5. The dispersion medium may be absolute ethanol. The mass ratio of the synthesized powder, the ball milling medium and the absolute ethyl alcohol in the ball milling process can be changed according to the requirement. For example, synthetic powders: ball milling medium: the mass ratio of the absolute ethyl alcohol can be 1:4.5:1.8. the ball milling speed can be 400-500 rpm. The ball milling time can be 4 to 6 hours. And (5) drying after fine grinding.
Adding a binder for granulating. The binder used for granulation may be an aqueous solution of polyvinyl alcohol (PVA) having a concentration of 5 to 7wt%. As an example, the concentration of the aqueous polyvinyl alcohol solution is 7wt%. The binder may be added in an amount of 6 to 7wt%, for example 6%, based on the weight of the ceramic powder. The granulation may be followed by aging for a period of time. The aging time may be 24 hours. And (5) aging and then compacting and forming. Green bodies of the desired dimensions can be produced by dry press forming. The pressing pressure may be 1 to 3MPa, for example 1.5MPa.
And (3) performing plastic removal and sintering on the ceramic green body to obtain the silver niobate-based ceramic material.
The temperature of plastic discharge is 700-800 ℃ and the time is 2-3 hours. The atmosphere for plastic discharge is oxygen atmosphere. In some embodiments, the plastic removal conditions may be: heating to 700 ℃ at a heating rate of not higher than 2 ℃/min under an oxygen atmosphere, preserving heat for 2 hours, and cooling to room temperature along with a furnace.
Sintering the ceramic biscuit after plastic removal in oxygen atmosphere. The sintering temperature is 980-1060 ℃, and the heat preservation time is 2 hours. Preferably, the temperature rise rate of the sintering is 2 ℃/min.
According to the preparation process of the invention, the ceramic sample with the average grain size of 400 nm-3 μm is obtained by controlling the sintering temperature within 980-1060 ℃. The smaller grain size is beneficial to improving the compressive strength of the ceramic sample, so that the energy storage density can be improved.
Through tests, the silver niobate-based relaxation type ternary solid solution ceramic material with high energy storage characteristics has typical narrow oblique hysteresis loop characteristics at room temperature. In some technical schemes, the breakdown electric field of the silver niobate-based relaxation type ternary solid solution ceramic material with high energy storage property is 444-489 kV/cm; the recyclable energy storage density is 5.55-6.69J/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The energy storage efficiency is 53.7-76.9%. For example, the lead-free silver niobate-based relaxed energy storage ceramic material of the embodiments has a high saturation polarization (saturation polarization strength up to about 50 μC/cm) 2 ) Low remnant polarization (remnant polarization may be less than 4. Mu.C/cm 2 ) High compressive strength (breakdown field strength can reach 489 kV/cm), and the like.
Therefore, the silver niobate based relaxation type ternary solid solution ceramic material with high energy storage property can be prepared by adopting a solid phase reaction method, has simple preparation process and can realize 489kBreakdown field strength of V/cm, 6.69J/cm 3 And an energy storage density of 76.9%.
Also disclosed herein is a silver niobate-based relaxation type energy storage ceramic element, which is produced using the silver niobate-based relaxation type energy storage ceramic material. In one example, the ceramic material is processed to a desired size, cleaned (e.g., ultrasonically cleaned), dried, silver coated, and burned to produce a silver niobate-based relaxed energy storage ceramic element. The silver firing conditions may be incubation at 650 ℃ for 30 minutes. The temperature may be raised to 650 ℃ at a temperature rise rate of not more than 2 ℃/minute.
The present invention will be described in more detail by way of examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
The chemical formula of the silver niobate based relaxation type energy storage ceramic material for energy storage is (1-x) (0.7 AgNbO) 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Wherein x=0.18.
The silver niobate based relaxation type energy storage ceramic material for energy storage is prepared by adopting a solid phase sintering method. The method specifically comprises the following steps of: (1) According to the chemical formula (1-x) (0.7 AgNbO) 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 (x=0.18) for compounding. The raw materials are as follows: sodium carbonate with a purity of 99.8%, niobium pentoxide with a purity of 99.99%, silver oxide with a purity of 99.7%, bismuth oxide with a purity of 99.999%, titanium dioxide with a purity of 99.9%, strontium carbonate with a purity of 99.99%. The weighing was performed with an electronic balance to an accuracy of 0.001g.
(2) Mixing the weighed raw materials, putting the mixture into a nylon pot, adding absolute ethyl alcohol into the pot, taking zirconia balls as ball milling media, and putting the nylon pot on a planetary ball mill for mixing for 4 hours. Zirconia balls contain two different sizes: 6mm in diameter and 10mm in diameter. The mass ratio of the zirconia balls with the diameter of 6mm and the diameter of 10mm is 3:2. raw material powder: ball milling medium: the mass ratio of the absolute ethyl alcohol is 1:4.5:1.8. and (3) pouring out the mixture after ball milling is finished, drying the mixture in a baking oven, sieving the mixture by using a 40-mesh nylon sieve, and pressing the sieved mixed powder into a cylinder block with the size of 60mm diameter and the height of 20mm on a press machine. Synthesizing the cylindrical bulk for 4 hours at 870 ℃ in oxygen atmosphere, and then crushing and sieving with a 40-mesh sieve to obtain synthetic powder.
(3) And (3) putting the obtained powder into a nylon tank again, adding absolute ethyl alcohol with the height not higher than 2/3 of the height of the tank into the tank, and taking zirconia columns and zirconia balls with different sizes as ball milling media. The zirconia column had dimensions of 7.5mm diameter by 7.5mm height, and the zirconia balls had diameters of 6mm and 10mm. Zirconia column: zirconia balls with a diameter of 6 mm: the mass ratio of the zirconia balls with the diameter of 10mm is 1:1.5:1. synthesizing powder: ball milling medium: the mass ratio of the absolute ethyl alcohol is 1:4.5:1.8. the nylon pot is placed on a planetary ball mill to be mixed for 6 hours, then poured out and dried in a baking box, and then sieved by a 40-mesh nylon sieve to obtain fine powder.
(4) Adding 7wt% concentration water solution of polyvinyl alcohol into the fine powder, pelletizing, sieving with 40 mesh sieve, molding to obtain cylinder with size of 13mm diameter and 1mm height, and draining. The plastic discharging condition is that the temperature is raised to 700 ℃ at the temperature rising rate of not higher than 2 ℃/min under the oxygen atmosphere, and the plastic is kept for 2 hours and cooled to the room temperature along with the furnace.
(5) Sintering the blank body after plastic removal in an oxygen atmosphere, wherein the sintering temperature is 1010 ℃, the heat preservation time is 2 hours, and taking out the sample after naturally cooling to room temperature.
And processing, cleaning, drying and electrode-loading the sintered ceramic sample to obtain the ceramic element.
And carrying out X-ray diffraction test on the prepared silver niobate based relaxation type energy storage ceramic material. Figure 1 shows the X-ray diffraction pattern of example 1. The ceramic of example 1 is seen to be pure phase.
The surface of the prepared ceramic was observed. Fig. 2 shows a surface SEM picture of example 1. The ceramic is sintered compactly, and the grain size is smaller and is 1-1.5 mu m.
The prepared ceramic element is subjected to monopole electric hysteresis loop test at room temperature and 10Hz, the field intensity corresponding to the rightmost end of the electric hysteresis loop is breakdown field intensity, and the formula is adoptedObtaining an effective energy storage density according to the formula +.>And obtaining energy storage efficiency. The visible electric hysteresis loop is narrow and inclined, and the energy storage density is 5.55J/cm 3 The energy storage efficiency was 53.7%, and the result is shown in fig. 9.
Example 2
The chemical formula of the silver niobate based relaxation type energy storage ceramic material for energy storage is (1-x) (0.7 AgNbO) 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Wherein x=0.2. The procedure was the same as in example 1, except that x=0.2.
And carrying out X-ray diffraction test on the prepared silver niobate based relaxation type energy storage ceramic material. Figure 1 shows the X-ray diffraction pattern of example 2. The ceramic of example 2 is seen to be pure phase.
The surface of the prepared ceramic was observed. Fig. 3 shows a surface SEM picture of example 2. The ceramic is sintered compactly, and the grain size is smaller and is 1-1.5 mu m.
The dielectric properties were measured using a dielectric impedance spectrometer, and the results are shown in FIG. 7. Fig. 7 shows the change of dielectric constant with temperature, and it can be seen that the temperature stability of the electrical properties of example 2 is good.
The prepared ceramic element was subjected to a monopolar hysteresis loop test at room temperature, 10 Hz. The visible electric hysteresis loop is narrow and inclined, and the energy storage density is 6.54J/cm 3 The energy storage efficiency was 69.3%, and the result is shown in fig. 10.
Example 3
For storing energyThe chemical formula of the silver niobate based relaxation type energy storage ceramic material is (1-x) (0.7 AgNbO) 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Where x=0.22. The procedure was the same as in example 1, except that x=0.22 and the sintering temperature was 1000 ℃.
And carrying out X-ray diffraction test on the prepared silver niobate based relaxation type energy storage ceramic material. Figure 1 shows the X-ray diffraction pattern of example 3. The ceramic of example 3 is seen to be pure phase.
The surface of the prepared ceramic was observed. Fig. 4 shows a surface SEM picture of example 3. The ceramic is sintered compactly, and the grain size is smaller and is 0.5-1 mu m.
The prepared ceramic element was subjected to a monopolar hysteresis loop test at room temperature at 10 Hz. The visible electric hysteresis loop is narrow and inclined, and the energy storage density is 6.69J/cm 3 The energy storage efficiency was 76.9%, and the result is shown in fig. 11.
Example 4
The chemical formula of the silver niobate based relaxation type energy storage ceramic material for energy storage is (1-x) (0.7 AgNbO) 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Wherein x=0.25. The procedure was the same as in example 1, except that x=0.25 and the sintering temperature was 1000 ℃.
And carrying out X-ray diffraction test on the prepared silver niobate based relaxation type energy storage ceramic material. Figure 1 shows the X-ray diffraction pattern of example 4. The ceramic of example 4 is seen to be pure phase.
The prepared ceramic element was subjected to a monopolar hysteresis loop test at room temperature, 10 Hz. The visible electric hysteresis loop is narrow and inclined, and the energy storage density is 6.11J/cm 3 The energy storage efficiency was 74.2%, and the result is shown in fig. 12.
Comparative example 1
The ceramic material composition of this comparative example 1 was (1-x) (0.7 AgNbO 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Wherein x=0. The procedure was the same as in example 1, except that x=0.
The prepared ceramic material was subjected to an X-ray diffraction test. FIG. 1 shows the X-ray diffraction pattern of comparative example 1. The ceramic of comparative example 1 is seen to be pure phase.
The surface of the prepared ceramic was observed. Fig. 5 shows a surface SEM picture of comparative example 1. The ceramic is sintered compactly, and the grain size is larger and is 2-3 mu m.
The prepared ceramic element was subjected to a monopolar hysteresis loop test at room temperature, 10 Hz. It can be seen that the energy storage density is 1.15J/cm 3 The energy storage efficiency was 21.9%, and the result is shown in fig. 13.
Comparative example 2
The ceramic material composition of this comparative example 2 was (1-x) (0.7 AgNbO 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Wherein x=0.1. The procedure was the same as in example 1, except that x=0.1.
And carrying out X-ray diffraction test on the prepared ceramic material. FIG. 1 shows the X-ray diffraction pattern of comparative example 2. The ceramic of comparative example 2 is seen to be pure phase.
The surface of the prepared ceramic was observed. Fig. 6 shows a surface SEM picture of comparative example 2. The ceramic is sintered compactly, and the grain size is larger and is 1.5-2 mu m.
The prepared ceramic element was subjected to a monopolar hysteresis loop test at room temperature, 10 Hz. The visible electric hysteresis loop is square and straight, and the energy storage density is 3.51J/cm 3 The energy storage efficiency was 45.1%, and the result is shown in fig. 14.
Comparative example 3
The ceramic material composition of this comparative example 3 was (1-x) (0.7 AgNbO 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Wherein x=0.15. The procedure was the same as in example 1, except that x=0.15.
And carrying out X-ray diffraction test on the prepared ceramic material. FIG. 1 shows the X-ray diffraction pattern of comparative example 3. The ceramic of comparative example 3 is seen to be pure phase.
The dielectric properties were measured using a dielectric impedance spectrometer, and the results are shown in FIG. 8. FIG. 8 is a graph showing the change of dielectric constant with temperature, and it can be seen that the material is antiferroelectric M 2 And (3) phase (C).
For preparation ofThe ceramic element of (2) was subjected to a monopolar hysteresis loop test at room temperature, 10 Hz. The visible electric hysteresis loop is square and straight, and the energy storage density is 4.64J/cm 3 The energy storage efficiency was 48.9%, and the result is shown in fig. 15.
Fig. 16 is a graph showing the change in energy storage density and energy storage efficiency with x. It can be seen that the energy storage density and the energy storage efficiency are significantly improved when x=0.2, and the energy storage performance is slightly reduced when x=0.25 compared with x=0.22, (Sr) 0.7 Bi 0.2 )TiO 3 The energy storage performance is remarkably improved.
Table 1 shows the composition and performance parameters of silver niobate-based ceramics prepared by the invention:
as can be seen from fig. 1 to 16 and table 1, with (Sr 0.7 Bi 0.2 )TiO 3 The content is increased, and although each ceramic material is pure phase, the hysteresis loops of examples 1 to 4 are more narrowly inclined than those of comparative examples 1 to 3, and the energy storage density is from 1.15 to 4.64J/cm 3 Increasing to 5.55-6.69J/cm 3 The energy storage efficiency is increased from 21.9 to 48.9 percent to 53.7 to 76.9 percent, and (Sr) 0.7 Bi 0.2 )TiO 3 Obviously improves the energy storage performance of the ceramic, and has proper (Sr) 0.7 Bi 0.2 )TiO 3 The high energy storage performance can be obtained by introducing the energy storage material.
Claims (9)
1. The silver niobate based relaxation type ternary solid solution ceramic material with high energy storage property is characterized by comprising the following chemical components: (1-x) (0.7 AgNbO) 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Wherein x is more than or equal to 0 and less than or equal to 0.25.
2. The silver niobate-based relaxation type ternary solid solution ceramic material with high energy storage property according to claim 1, wherein x is more than or equal to 0.18 and less than or equal to 0.25.
3. According to claim 1 or 2The silver niobate based relaxation type ternary solid solution ceramic material with high energy storage property is characterized in that the breakdown electric field of the silver niobate based relaxation type ternary solid solution ceramic material with high energy storage property is 444-489 kV/cm; the recyclable energy storage density is 5.55-6.69J/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The energy storage efficiency is 53.7-76.9%.
4. A method for preparing the silver niobate-based relaxation type ternary solid solution ceramic material with high energy storage property according to any one of claims 1 to 3, wherein the preparation method comprises:
(1) According to the stoichiometric ratio (1-x) (0.7 AgNbO) 3 -0.3NaNbO 3 )-x(Sr 0.7 Bi 0.2 )TiO 3 Weighing silver oxide powder, niobium pentoxide powder, titanium dioxide powder, sodium carbonate powder, bismuth oxide powder and strontium titanate powder as raw material powder, mixing, calcining and finely grinding to obtain synthetic powder;
(2) Mixing the obtained synthetic powder with a binder, granulating, aging, sieving and forming to obtain a ceramic green body;
(3) And (3) performing plastic removal and sintering on the obtained ceramic green body to obtain the silver niobate-based relaxation type ternary solid solution ceramic material with high energy storage property.
5. The method according to claim 4, wherein in the step (1), the mixing is performed by ball milling; preferably, absolute ethyl alcohol is used as a dispersion medium, the ball milling rotating speed is 230-250 rpm, and the ball milling time is 4-6 hours; more preferably, the ball milling media are zirconia balls and/or zirconia columns.
6. The method according to claim 4 or 5, wherein in the step (1), the calcination atmosphere is an oxygen atmosphere, the calcination temperature is 850 to 870 ℃, and the calcination time is 2 to 4 hours.
7. The method according to any one of claims 4 to 6, wherein in the step (2), the binder is an aqueous solution of polyvinyl alcohol having a concentration of 5 to 7wt%; the addition amount of the binder is 6-7wt% of the mass of the synthesized powder; the sieved screen mesh is 20-80 meshes.
8. The method according to any one of claims 4 to 7, wherein in the step (3), the temperature of the plastic discharge is 700 to 800 ℃ for 2 to 3 hours.
9. The method according to any one of claims 4 to 8, wherein in step (3), the sintering temperature is 980 ℃ to 1060 ℃ for 2 to 3 hours; the temperature rising rate of the sintering is not higher than 2 ℃/min.
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