CN116854469A - Sodium bismuth titanate-based high-entropy medium energy storage ceramic material and preparation method and application thereof - Google Patents
Sodium bismuth titanate-based high-entropy medium energy storage ceramic material and preparation method and application thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 66
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 47
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 218
- 239000011734 sodium Substances 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 37
- 238000000498 ball milling Methods 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 238000005498 polishing Methods 0.000 claims abstract description 19
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 13
- 239000003292 glue Substances 0.000 claims abstract description 13
- 238000007599 discharging Methods 0.000 claims abstract description 9
- 239000003990 capacitor Substances 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims description 86
- 238000010438 heat treatment Methods 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000227 grinding Methods 0.000 claims description 18
- 238000007873 sieving Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 244000137852 Petrea volubilis Species 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001465 metallisation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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Abstract
The invention provides a sodium bismuth titanate-based high-entropy medium energy storage ceramic material, which comprises the following components in percentage by weight: (Bi) 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 . The preparation method comprises the following steps: drying the dried Na 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw material, srCO 3 Raw materials, nb 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 The raw materials are subjected to ball milling after being proportioned, and then are subjected to presintering, secondary ball milling, tabletting, glue discharging, sintering, polishing and surface treatmentAnd (3) metallizing to obtain the sodium bismuth titanate-based high-entropy medium energy storage ceramic material, and providing application for preparing the pulse capacitor. The sodium bismuth titanate-based high-entropy medium energy storage ceramic material prepared by the invention has the advantages of excellent energy storage performance, simple preparation process, good repeatability and low cost, and is suitable for industrialization.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a sodium bismuth titanate-based high-entropy medium energy storage ceramic material, and a preparation method and application thereof.
Background
With the development of material science and technology and 5G and 6G mobile communication, electronic components tend to be miniaturized, light-weighted and intelligent, and high-end dielectric capacitors with high energy storage density and low loss are urgently needed. Bismuth sodium titanate ceramic is considered as one of the most commercially applicable lead-free environment-friendly materials as an important system for dielectric capacitor materials because of its wide band gap (large breakdown electric field), non-volatile K element (easy preparation) and low bulk density (light weight). However, based on the conventional doping and defect engineering strategies, a large ΔP (Pmax-Pr) and a high breakdown field strength (Eb) can be rarely realized in the bismuth sodium titanate ceramic material at the same time, so that the bismuth sodium titanate ceramic material is difficult to meet the practical application.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the sodium bismuth titanate-based high-entropy medium energy storage ceramic material, and the preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme: the sodium bismuth titanate-based high-entropy medium energy storage ceramic material has the composition formula:
(Bi 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 。
the embodiment also provides a method for preparing the sodium bismuth titanate-based high-entropy medium energy storage ceramic material, which comprises the following steps:
s1, baking materials: respectively Na 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw materials and SrCO 3 Drying the raw materials in strips at 300 ℃ for 6 hours respectively;
nb is set to 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 Drying the raw materials in strips at 900 ℃ for 4 hours respectively;
the Na is 2 CO 3 The purity of the raw material is 99.8%, and the Bi is 2 O 3 The purity of the raw material is 99 percent, and the CaCO 3 The purity of the raw material is 99%, the BaCO 3 The purity of the raw material is 99%, the SrCO 3 The purity of the raw material is 99%, the Nb 2 O 5 The purity of the raw material is 99.5%, and the TiO is 2 The purity of the raw material is 98%, ta is 2 O 5 The purity of the starting material was 99.99%, the ZrO 2 The purity of the raw material is 99%, the purity of the MgO raw material is 98.5%, and the SnO is 2 The purity of the raw materials is 99.5%;
s2, proportioning: drying the dried Na in S1 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw material, srCO 3 Raw materials, nb 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 Raw materials according to (Bi) 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 Respectively weighing and uniformly mixing stoichiometric ratios of (1) to obtain a premix, adding agate balls and absolute ethyl alcohol, ball-milling for 6-10 hours at a speed of 300-400 r/min in a planetary ball mill, separating the agate balls, drying for 10-24 hours at a temperature of 70-120 ℃, and sieving with a 120-mesh sieve after grinding to obtain a raw material mixture;
s3, presintering: heating the raw material mixture obtained in the step S2 from normal temperature to 850-950 ℃ at a heating rate of 3-5 ℃/min, presintering at a constant temperature for 2-4 hours, naturally cooling to the room temperature, and grinding to obtain presintering powder;
s4, secondary ball milling: adding agate balls and absolute ethyl alcohol into the pre-sintered powder obtained in the step S3, ball milling for 6-10 hours, separating the agate balls, drying for 10-24 hours at the temperature of 70-120 ℃, grinding, and sieving with a 180-mesh sieve to obtain ball-milled pre-sintered powder;
s5, tabletting, namely adding 6% polyvinyl alcohol aqueous solution into the ball-milled pre-sintered powder obtained in the step S4, granulating, sieving with a 40-mesh sieve to obtain a quicksand-shaped spherical powder substance, and maintaining the pressure for 10S to 60S under the unidirectional pressure condition of 100MPa to 200MPa to obtain a disc-shaped ceramic blank;
s6, glue discharging: raising the temperature of the wafer-shaped ceramic blank obtained in the step S5 to 500-600 ℃ at a heating rate of 1-3 ℃/min, preserving heat for 1-3 h, and naturally cooling to room temperature to obtain a wafer-shaped ceramic blank after glue discharge;
s7, sintering: sintering the disc-shaped ceramic blank body with the adhesive discharged obtained in the step S5 to obtain a sintered ceramic blank body; the sintering conditions are as follows: firstly, heating from room temperature to 1160-1220 ℃ at a heating rate of 3-5 ℃/min, sintering at constant temperature for 2-3 h, and then cooling to room temperature at a cooling rate of 5 ℃/min;
s8, polishing: polishing the upper and lower surfaces of the sintered ceramic blank obtained in the step S7 by using 600-mesh sand paper, polishing the upper and lower surfaces by using 2000-mesh sand paper and silicon carbide to a thickness of 0.3-0.5 mm, putting the ceramic blank into deionized water, ultrasonically cleaning the ceramic blank, and drying the ceramic blank to obtain a polished ceramic blank;
s9, surface metallization: and (3) uniformly coating silver paste with the thickness of 0.01-0.03 mm on the upper and lower surfaces of the polished ceramic blank obtained in the step (S8), then placing the ceramic blank in a resistance furnace, heating to the temperature of 850 ℃ at the heating rate of 3-6 ℃/min, preserving heat for 10min, and naturally cooling to the room temperature to obtain the sodium bismuth titanate-based high-entropy medium energy storage ceramic material.
Preferably, the dosage ratio of premix, agate balls and absolute ethanol in S2 is 0.30g:1g:0.45mL.
Preferably, the dosage ratio of the pre-sintered powder, the agate balls and the absolute ethyl alcohol in the S4 is 0.28g to 1g:0.40mL.
Preferably, in the step S5, the mass ratio of the 6% polyvinyl alcohol aqueous solution to the pre-sintered powder after ball milling is (5% -10%): 1.
preferably, the ultrasonic cleaning in S8 is performed for 10min to 20min.
Preferably, the sodium bismuth titanate-based high-entropy medium energy storage ceramic material (Bi 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 The breakdown field strength is 359-370 kV/cm, and the energy storage density is W rec 4.16 to 4.33J/cm 3 The energy storage efficiency eta is 89.7 to 90.1 percent, and has excellent temperature stability (W rec Changing the value in the temperature range of 25-200 DEG C<7%), frequency stability Performance (W) rec Varying values in the range of 1-200Hz<3%) and excellent fatigue characteristics (W rec At 10 6 Values of variation over a cyclic range<3％)。
The invention also provides application of the sodium bismuth titanate-based high-entropy medium energy storage ceramic material prepared by the method, and the sodium bismuth titanate-based high-entropy medium energy storage ceramic material is used for preparing pulse capacitors.
Compared with the prior art, the invention has the following advantages:
the high-entropy ceramic prepared by the invention can obtain the maximum energy storage density (breakdown field strength E b Reaches 359-370 kV/cm, and energy storage density W rec Can reach 4.16-4.33J/cm 3 The energy storage efficiency eta is 89.7 to 90.1 percent), and the temperature stability (W) is excellent rec Changing the value in the temperature range of 25-200 DEG C<7%), frequency stability Performance (W) rec Varying values in the range of 1-200Hz<3%) and excellent fatigue characteristics (W rec At 10 6 Values of variation over a cyclic range<3 percent), has strong practicability, is easy for routine batch production, is lead-free high-entropy medium energy storage ceramic with excellent performance, and can be used for high-power devices such as pulse capacitors and the like.
The invention is described in further detail below with reference to the drawings and examples.
Drawings
FIG. 1 is an XRD pattern of the ceramic body polished in S8 of examples 1-4 of the present invention.
FIG. 2 is an SEM scan of the ceramic body of S7 of examples 1-4 of the invention.
FIG. 3 is a P-E characteristic diagram of the sodium bismuth titanate based high entropy medium energy storage ceramic material of example 2 of the present invention.
Fig. 4 is a graph of the energy storage performance temperature stability of the sodium bismuth titanate based high entropy medium energy storage ceramic material of example 2 of the present invention.
Fig. 5 is a graph of the frequency stability of the energy storage performance of the sodium bismuth titanate based high entropy medium energy storage ceramic material of example 2 of the present invention.
FIG. 6 is a graph showing the fatigue performance test of the energy storage performance of the sodium bismuth titanate based high entropy medium energy storage ceramic material of example 2 of the present invention.
Detailed Description
Example 1
The sodium bismuth titanate-based high-entropy medium energy storage ceramic material of the embodiment has the composition formula:
(Bi 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 。
the embodiment also provides a method for preparing the sodium bismuth titanate-based high-entropy medium energy storage ceramic material, which comprises the following steps:
s1, baking materials: respectively Na 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw materials and SrCO 3 Drying the raw materials in strips at 300 ℃ for 6 hours respectively;
nb is set to 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 Drying the raw materials in strips at 900 ℃ for 4 hours respectively;
the Na is 2 CO 3 The purity of the raw material is 99.8Percent, purchased from the Bi 2 O 3 The purity of the raw material is 99 percent, and the CaCO 3 The purity of the raw material is 99%, the BaCO 3 The purity of the raw material is 99%, the SrCO 3 The purity of the raw material is 99%, the Nb 2 O 5 The purity of the raw material is 99.5%, and the TiO is 2 The purity of the raw material is 98%, ta is 2 O 5 The purity of the starting material was 99.99%, the ZrO 2 The purity of the raw material is 99%, the purity of the MgO raw material is 98.5%, and the SnO is 2 The purity of the raw materials is 99.5%; all the raw materials are purchased from national medicine group chemical reagent limited company;
s2, proportioning: drying the dried Na in S1 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw material, srCO 3 Raw materials, nb 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 Raw materials according to (Bi) 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 Respectively weighing and uniformly mixing stoichiometric ratios of (1) to obtain a premix, adding agate balls and absolute ethyl alcohol, ball-milling for 6 hours at a speed of 400r/min in a planetary ball mill, separating the agate balls, drying for 24 hours at a temperature of 70 ℃, grinding, and sieving with a 120-mesh sieve to obtain a raw material mixture; the dosage ratio of the premix, the agate balls and the absolute ethyl alcohol is 0.30g to 1g:0.45mL;
s3, presintering: heating the raw material mixture obtained in the step S2 from normal temperature to 950 ℃ at a heating rate of 5 ℃/min, presintering at a constant temperature for 2 hours, naturally cooling to the room temperature, and grinding to obtain presintering powder;
s4, secondary ball milling: adding agate balls and absolute ethyl alcohol into the pre-sintered powder obtained in the step S3, ball milling for 6 hours, separating the agate balls, drying for 24 hours at the temperature of 70 ℃, grinding, and sieving with a 180-mesh sieve to obtain ball-milled pre-sintered powder; the dosage ratio of the presintered powder to the agate balls to the absolute ethyl alcohol is 0.28g to 1g:0.40mL;
s5, tabletting, namely adding 6% polyvinyl alcohol aqueous solution into the ball-milled pre-sintered powder obtained in the step S4, granulating, sieving with a 40-mesh sieve to obtain a quicksand-shaped spherical powder substance, and maintaining the pressure for 60S under a unidirectional pressure condition of 100MPa to obtain a disc-shaped ceramic blank; the mass ratio of the 6% polyvinyl alcohol aqueous solution to the presintered powder after ball milling is 10%:1, a step of;
s6, glue discharging: raising the temperature of the wafer-shaped ceramic blank obtained in the step S5 to 600 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, decomposing and discharging PVA, and naturally cooling to room temperature to obtain a wafer-shaped ceramic blank after glue discharge;
s7, sintering: sintering the disc-shaped ceramic blank body with the adhesive discharged obtained in the step S5 to obtain a sintered ceramic blank body; the sintering conditions are as follows: firstly, heating from room temperature to 1160 ℃ at a heating rate of 3 ℃/min, sintering at constant temperature for 3 hours, and then cooling to room temperature at a cooling rate of 5 ℃/min;
s8, polishing: polishing the upper and lower surfaces of the sintered ceramic blank obtained in the step S7 by using 600-mesh sand paper, polishing the upper and lower surfaces to a thickness of 0.3mm by using 2000-mesh sand paper and silicon carbide, placing the ceramic blank into deionized water, ultrasonically cleaning the ceramic blank for 10min, and drying the ceramic blank to obtain a polished ceramic blank;
XRD testing of the polished ceramic body was performed by using a German Brookfield D8 Advanced type diffractometer, SEM scanning test was performed on the surface of the ceramic sample by using a Japanese Hitachi S-4800 type scanning electron microscope, and the results are shown in FIGS. 1 to 2, and the prepared (Bi 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 The high-entropy medium energy storage ceramic material has a pure perovskite structure, the average grain size is 2.6 mu m, and the grain distribution is compact;
s9, surface metallization: and (3) uniformly coating silver paste with the thickness of 0.01mm on the upper and lower surfaces of the polished ceramic blank obtained in the step (S8), then placing the ceramic blank in a resistance furnace, heating to 850 ℃ at the heating rate of 3 ℃/min, preserving heat for 10min, and naturally cooling to room temperature to obtain the sodium bismuth titanate-based high-entropy medium energy storage ceramic material.
The bismuth sodium titanate-based high-entropy medium energy storage ceramic material (Bi) prepared in the embodiment is respectively prepared by adopting an RK2670YM pressure-resistant instrument and a German aixACCT-TF 3000 ferroelectric tester 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 The breakdown field strength, P-E characteristics and energy storage performance were tested and the results are shown in table 1. And W is rec Changing the value in the temperature range of 25-200 DEG C<6.5％、W rec Varying values in the range of 1-200Hz<2.7％，W rec At 10 6 Values of variation over a cyclic range<2.9％。
Table 1 performance test of example 1
Example 2
The sodium bismuth titanate-based high-entropy medium energy storage ceramic material of the embodiment has the composition formula:
(Bi 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 。
the embodiment also provides a method for preparing the sodium bismuth titanate-based high-entropy medium energy storage ceramic material, which comprises the following steps:
s1, baking materials: respectively Na 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw materials and SrCO 3 Drying the raw materials in strips at 300 ℃ for 6 hours respectively;
nb is set to 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 Drying the raw materials in strips at 900 ℃ for 4 hours respectively;
the Na is 2 CO 3 The purity of the raw material was 99.8%, purchased from the Bi 2 O 3 The purity of the raw material is 99 percent, and the CaCO 3 The purity of the raw material is 99%, the BaCO 3 The purity of the raw material is 99%, the SrCO 3 The purity of the raw material is 99%, the Nb 2 O 5 The purity of the raw material is 99.5%, and the TiO is 2 The purity of the raw material is 98%, ta is 2 O 5 The purity of the starting material was 99.99%, the ZrO 2 The purity of the raw material is 99%, the purity of the MgO raw material is 98.5%, and the SnO is 2 The purity of the raw materials is 99.5%; all the raw materials are purchased from national medicine group chemical reagent limited company;
s2, proportioning: drying the dried Na in S1 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw material, srCO 3 Raw materials, nb 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 Raw materials according to (Bi) 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 Respectively weighing and uniformly mixing stoichiometric ratios of (1) to obtain a premix, adding agate balls and absolute ethyl alcohol, ball-milling for 8 hours at a speed of 350r/min in a planetary ball mill, separating the agate balls, drying for 18 hours at a temperature of 100 ℃, grinding, and sieving with a 120-mesh sieve to obtain a raw material mixture; the dosage ratio of the premix, the agate balls and the absolute ethyl alcohol is 0.30g to 1g:0.45mL;
s3, presintering: heating the raw material mixture obtained in the step S2 from normal temperature to 850 ℃ at a heating rate of 5 ℃/min, presintering at a constant temperature for 2 hours, naturally cooling to the room temperature, and grinding to obtain presintering powder;
s4, secondary ball milling: adding agate balls and absolute ethyl alcohol into the pre-sintered powder obtained in the step S3, ball milling for 8 hours, separating the agate balls, drying for 18 hours at the temperature of 100 ℃, grinding, and sieving with a 180-mesh sieve to obtain ball-milled pre-sintered powder; the dosage ratio of the presintered powder to the agate balls to the absolute ethyl alcohol is 0.28g to 1g:0.40mL;
s5, tabletting, namely adding 6% polyvinyl alcohol aqueous solution into the ball-milled pre-sintered powder obtained in the step S4, granulating, sieving with a 40-mesh sieve to obtain a quicksand-shaped spherical powder substance, and maintaining the pressure for 60S under a unidirectional pressure condition of 200MPa to obtain a disc-shaped ceramic blank; the mass ratio of the 6% polyvinyl alcohol aqueous solution to the presintered powder after ball milling is 8%:1, a step of;
s6, glue discharging: raising the temperature of the wafer-shaped ceramic blank obtained in the step S5 to 550 ℃ at a heating rate of 3 ℃/min, preserving heat for 3 hours, decomposing and discharging PVA, and naturally cooling to room temperature to obtain a wafer-shaped ceramic blank after glue discharge;
s7, sintering: sintering the disc-shaped ceramic blank body with the adhesive discharged obtained in the step S5 to obtain a sintered ceramic blank body; the sintering conditions are as follows: firstly, heating from room temperature to 1180 ℃ at a heating rate of 5 ℃/min, sintering at constant temperature for 2 hours, and then cooling to room temperature at a cooling rate of 5 ℃/min;
s8, polishing: polishing the upper and lower surfaces of the sintered ceramic blank obtained in the step S7 by using 600-mesh sand paper, polishing the upper and lower surfaces to a thickness of 0.35mm by using 2000-mesh sand paper and silicon carbide, placing the ceramic blank into deionized water, ultrasonically cleaning the ceramic blank for 15min, and drying the ceramic blank to obtain a polished ceramic blank;
XRD testing of the polished ceramic body of this example was performed by using a Bluck D8 Advanced type diffractometer, and SEM scanning test was performed on the surface of the ceramic sample by using a Japanese Hitachi S-4800 type scanning electron microscope, the results of which are shown in FIGS. 1 to 2, and the (Bi) 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 The high-entropy medium energy storage ceramic material has a pure perovskite structure, the average grain size is 2.1 mu m, and the grain distribution is compact.
S9, surface metallization: and (3) uniformly coating silver paste with the thickness of 0.02mm on the upper and lower surfaces of the polished ceramic blank obtained in the step (S8), then placing the ceramic blank in a resistance furnace, heating to 850 ℃ at the heating rate of 5 ℃/min, preserving heat for 10min, and naturally cooling to room temperature to obtain the sodium bismuth titanate-based high-entropy medium energy storage ceramic material.
The bismuth sodium titanate-based high-entropy medium energy storage ceramic material (Bi) prepared in the embodiment is respectively prepared by adopting an RK2670YM pressure-resistant instrument and a German aixACCT-TF 3000 ferroelectric tester 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 The breakdown field strength, P-E characteristics and energy storage performance were tested and the results are shown in table 2. The P-E curve, the energy storage performance stability and the fatigue performance curve are shown in FIGS. 3 to 6, which have excellent temperature stability (W rec Changing the value in the temperature range of 25-200 DEG C<6.6%), frequency stability (W rec Varying values in the range of 1-200Hz<3%) and excellent fatigue characteristics (W rec At 10 6 Values of variation over a cyclic range<2.8％)
Table 2 performance test of example 2
| Breakdown field strength | Maximum polarization intensity | Residual polarization intensity | Effective energy storage density | Energy storage efficiency |
| 370kV/cm | 27.8μC/cm 2 | 0.94μC/cm 2 | 4.33J/cm 3 | 89.7％ |
The sodium bismuth titanate-based high-entropy medium energy storage ceramic material is used for preparing high-power devices of pulse capacitors. The sodium bismuth titanate-based high-entropy medium energy storage ceramic prepared by the embodiment has the advantages of electromagnetic interference resistance, short charge and discharge time, long storage time, no degradation and aging, high breakdown field strength, larger energy storage density and quite long service life>10 6 ) The method is favorable for the development requirements of miniaturization and light weight of the energy system, and plays an important role in the fields of national defense, scientific experiments, industry and agriculture, medicine and the like.
Example 3
The sodium bismuth titanate-based high-entropy medium energy storage ceramic material of the embodiment has the composition formula:
(Bi 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 。
the embodiment also provides a method for preparing the sodium bismuth titanate-based high-entropy medium energy storage ceramic material, which comprises the following steps:
s1, baking materials: respectively Na 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw materials and SrCO 3 Drying the raw materials in strips at 300 ℃ for 6 hours respectively;
nb is set to 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 Drying the raw materials in strips at 900 ℃ for 4 hours respectively;
the Na is 2 CO 3 The purity of the raw material was 99.8%, purchased from the Bi 2 O 3 Purity of the raw materials99% of the CaCO 3 The purity of the raw material is 99%, the BaCO 3 The purity of the raw material is 99%, the SrCO 3 The purity of the raw material is 99%, the Nb 2 O 5 The purity of the raw material is 99.5%, and the TiO is 2 The purity of the raw material is 98%, ta is 2 O 5 The purity of the starting material was 99.99%, the ZrO 2 The purity of the raw material is 99%, the purity of the MgO raw material is 98.5%, and the SnO is 2 The purity of the raw materials is 99.5%; all the raw materials are purchased from national medicine group chemical reagent limited company;
s2, proportioning: drying the dried Na in S1 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw material, srCO 3 Raw materials, nb 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 Raw materials according to (Bi) 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 Respectively weighing and uniformly mixing stoichiometric ratios of (1) to obtain a premix, adding agate balls and absolute ethyl alcohol, ball-milling for 7 hours at the speed of 330r/min in a planetary ball mill, separating the agate balls, drying for 20 hours at the temperature of 90 ℃, grinding, and sieving with a 120-mesh sieve to obtain a raw material mixture; the dosage ratio of the premix, the agate balls and the absolute ethyl alcohol is 0.30g to 1g:0.45mL;
s3, presintering: heating the raw material mixture obtained in the step S2 from normal temperature to 900 ℃ at a heating rate of 4 ℃/min, presintering at a constant temperature for 3 hours, naturally cooling to the room temperature, and grinding to obtain presintering powder;
s4, secondary ball milling: adding agate balls and absolute ethyl alcohol into the pre-sintered powder obtained in the step S3, ball-milling for 7 hours, separating the agate balls, drying for 20 hours at the temperature of 90 ℃, grinding, and sieving with a 180-mesh sieve to obtain ball-milled pre-sintered powder; the dosage ratio of the presintered powder to the agate balls to the absolute ethyl alcohol is 0.28g to 1g:0.40mL;
s5, tabletting, namely adding 6% polyvinyl alcohol aqueous solution into the ball-milled pre-sintered powder obtained in the step S4, granulating, sieving with a 40-mesh sieve to obtain a quicksand-shaped spherical powder substance, and maintaining the pressure for 30S under a unidirectional pressure condition of 150MPa to obtain a disc-shaped ceramic blank; the mass ratio of the 6% polyvinyl alcohol aqueous solution to the presintered powder after ball milling is 7%:1, a step of;
s6, glue discharging: raising the temperature of the wafer-shaped ceramic blank obtained in the step S5 to 575 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain a wafer-shaped ceramic blank after glue discharge;
s7, sintering: sintering the disc-shaped ceramic blank body with the adhesive discharged obtained in the step S5 to obtain a sintered ceramic blank body; the sintering conditions are as follows: firstly, heating from room temperature to 1200 ℃ at a heating rate of 4 ℃/min, sintering at constant temperature for 2.5 hours, and then cooling to room temperature at a cooling rate of 5 ℃/min;
s8, polishing: polishing the upper and lower surfaces of the sintered ceramic blank obtained in the step S7 by using 600-mesh sand paper, polishing the upper and lower surfaces to a thickness of 0.4mm by using 2000-mesh sand paper and silicon carbide, placing the ceramic blank into deionized water, ultrasonically cleaning the ceramic blank for 20min, and drying the ceramic blank to obtain a polished ceramic blank;
XRD testing of the polished ceramic body of this example was performed by using a Bluck D8 Advanced type diffractometer, and SEM scanning test was performed on the surface of the ceramic sample by using a Japanese Hitachi S-4800 type scanning electron microscope, the results of which are shown in FIGS. 1 to 2, and the (Bi) 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 The high-entropy medium energy storage ceramic material has a pure perovskite structure, the average grain size is 3.0 mu m, and the grain distribution is compact.
S9, surface metallization: and (3) uniformly coating silver paste with the thickness of 0.02mm on the upper and lower surfaces of the polished ceramic blank obtained in the step (S8), then placing the ceramic blank in a resistance furnace, heating to 850 ℃ at the heating rate of 4 ℃/min, preserving heat for 10min, and naturally cooling to room temperature to obtain the sodium bismuth titanate-based high-entropy medium energy storage ceramic material.
Prepared in this exampleBismuth sodium titanate-based high-entropy medium energy storage ceramic material (Bi) 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 The breakdown field strength, P-E characteristics and energy storage performance results are shown in table 3. And W is rec Changing the value in the temperature range of 25-200 DEG C<6.9％、W rec Varying values in the range of 1-200Hz<2.9％，W rec At 10 6 Values of variation over a cyclic range<2.9％。
TABLE 3 Performance test of example 3
| Breakdown field strength | Maximum polarization intensity | Residual polarization intensity | Effective energy storage density | Energy storage efficiency |
| 365kV/cm | 27.5μC/cm 2 | 0.98μC/cm 2 | 4.22J/cm 3 | 89.9％ |
Example 4
The sodium bismuth titanate-based high-entropy medium energy storage ceramic material of the embodiment has the composition formula:
(Bi 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 。
the embodiment also provides a method for preparing the sodium bismuth titanate-based high-entropy medium energy storage ceramic material, which comprises the following steps:
s1, baking materials: respectively Na 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw materials and SrCO 3 Drying the raw materials in strips at 300 ℃ for 6 hours respectively;
nb is set to 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 Drying the raw materials in strips at 900 ℃ for 4 hours respectively;
the Na is 2 CO 3 The purity of the raw material was 99.8%, purchased from the Bi 2 O 3 The purity of the raw material is 99 percent, and the CaCO 3 The purity of the raw material is 99%, the BaCO 3 The purity of the raw material is 99%, the SrCO 3 The purity of the raw material is 99%, the Nb 2 O 5 The purity of the raw material is 99.5%, and the TiO is 2 The purity of the raw material is 98%, ta is 2 O 5 The purity of the starting material was 99.99%, the ZrO 2 The purity of the raw material is 99%, the purity of the MgO raw material is 98.5%, and the SnO is 2 The purity of the raw materials is 99.5%; all the raw materials are purchased from national medicine group chemical reagent limited company;
s2, proportioning: drying the dried Na in S1 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw material, srCO 3 Raw materials, nb 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 Raw materials according to (Bi) 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 Respectively weighing and uniformly mixing stoichiometric ratios of (1) to obtain a premix, adding agate balls and absolute ethyl alcohol, ball-milling for 10 hours at a speed of 300r/min in a planetary ball mill, separating the agate balls, drying for 10 hours at 120 ℃, grinding, and sieving with a 120-mesh sieve to obtain a raw material mixture; the dosage ratio of the premix, the agate balls and the absolute ethyl alcohol is 0.30g to 1g:0.45mL;
s3, presintering: heating the raw material mixture obtained in the step S2 from normal temperature to 850 ℃ at a heating rate of 3 ℃/min, presintering at a constant temperature for 4 hours, naturally cooling to the room temperature, and grinding to obtain presintering powder;
s4, secondary ball milling: adding agate balls and absolute ethyl alcohol into the pre-sintered powder obtained in the step S3, ball milling for 10 hours, separating the agate balls, drying for 10 hours at 120 ℃, grinding, and sieving with a 180-mesh sieve to obtain ball-milled pre-sintered powder; the dosage ratio of the presintered powder to the agate balls to the absolute ethyl alcohol is 0.28g to 1g:0.40mL;
s5, tabletting, namely adding 6% polyvinyl alcohol aqueous solution into the ball-milled pre-sintered powder obtained in the step S4, granulating, sieving with a 40-mesh sieve to obtain a quicksand-shaped spherical powder substance, and maintaining the pressure for 10S under the unidirectional pressure condition of 200MPa to obtain a disc-shaped ceramic blank; the mass ratio of the 6% polyvinyl alcohol aqueous solution to the presintered powder after ball milling is 5%:1, a step of;
s6, glue discharging: raising the temperature of the wafer-shaped ceramic blank obtained in the step S5 to 500 ℃ at a heating rate of 1 ℃/min, preserving heat for 3 hours, and naturally cooling to room temperature to obtain a wafer-shaped ceramic blank after glue discharge;
s7, sintering: sintering the disc-shaped ceramic blank body with the adhesive discharged obtained in the step S5 to obtain a sintered ceramic blank body; the sintering conditions are as follows: heating from room temperature to 1220 ℃ at a heating rate of 5 ℃/min, sintering at constant temperature for 2 hours, and cooling to room temperature at a cooling rate of 5 ℃/min;
s8, polishing: polishing the upper and lower surfaces of the sintered ceramic blank obtained in the step S7 by using 600-mesh sand paper, polishing the upper and lower surfaces to a thickness of 0.5mm by using 2000-mesh sand paper and silicon carbide, placing the ceramic blank into deionized water, ultrasonically cleaning the ceramic blank for 20min, and drying the ceramic blank to obtain a polished ceramic blank;
XRD testing of the polished ceramic body of this example was performed by using a Bluck D8 Advanced type diffractometer, and SEM scanning test was performed on the surface of the ceramic sample by using a Japanese Hitachi S-4800 type scanning electron microscope, the results of which are shown in FIGS. 1 to 2, and the (Bi) 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 The high-entropy medium energy storage ceramic material has a pure perovskite structure, the average grain size is 3.5 mu m, and the grain distribution is compact.
S9, surface metallization: and (3) uniformly coating silver paste with the thickness of 0.03mm on the upper and lower surfaces of the polished ceramic blank obtained in the step (S8), then placing the ceramic blank in a resistance furnace, heating to 850 ℃ at the heating rate of 6 ℃/min, preserving heat for 10min, and naturally cooling to room temperature to obtain the sodium bismuth titanate-based high-entropy medium energy storage ceramic material.
Sodium bismuth titanate-based high-entropy medium energy storage ceramic material (Bi) prepared in this example 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 The breakdown field strength, P-E characteristics and energy storage performance results are shown in table 4. And W is rec Changing the value in the temperature range of 25-200 DEG C<7％、W rec Varying values in the range of 1-200Hz<3％，W rec At 10 6 Values of variation over a cyclic range<3％。
Table 4 performance test of example 4
The sodium bismuth titanate-based high-entropy medium energy storage ceramic material is used for preparing pulse capacitors.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (7)
1. The bismuth sodium titanate-based high-entropy medium energy storage ceramic material is characterized by comprising the following components in percentage by weight:
(Bi 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 。
2. a method for preparing the sodium bismuth titanate based high entropy medium energy storage ceramic material as claimed in claim 1, which is characterized in that the method comprises the following steps:
s1, baking materials: respectively Na 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw materials and SrCO 3 Drying the raw materials in strips at 300 ℃ for 6 hours respectively;
nb is set to 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 Drying the raw materials in strips at 900 ℃ for 4 hours respectively;
the Na is 2 CO 3 The purity of the raw material is 99.8%, and the Bi is 2 O 3 The purity of the raw material is 99 percent, and the CaCO 3 The purity of the raw material is 99%, the BaCO 3 The purity of the raw material is 99%, the SrCO 3 The purity of the raw material is 99%, the Nb 2 O 5 The purity of the raw material is 99.5%, and the TiO is 2 The purity of the raw materials is 98 percent, the obtainedThe Ta is 2 O 5 The purity of the starting material was 99.99%, the ZrO 2 The purity of the raw material is 99%, the purity of the MgO raw material is 98.5%, and the SnO is 2 The purity of the raw materials is 99.5%;
s2, proportioning: drying the dried Na in S1 2 CO 3 Raw materials, bi 2 O 3 Raw materials, caCO 3 Raw material, baCO 3 Raw material, srCO 3 Raw materials, nb 2 O 5 Raw materials, tiO 2 Raw material, ta 2 O 5 Raw material, zrO 2 Raw materials, mgO raw material and SnO 2 The raw materials are according to the following steps
(Bi 0.5 Na 0.5 ) 0.8 Sr 0.07 Ba 0.07 Ca 0.06 Ti 0.75 (Nb 0.05 Mg 0.05 Ta 0.05 Zr 0.05 Sn 0.05 )O 3 Respectively weighing and uniformly mixing stoichiometric ratios of (1) to obtain a premix, adding agate balls and absolute ethyl alcohol, ball-milling for 6-10 hours at a speed of 300-400 r/min in a planetary ball mill, separating the agate balls, drying for 10-24 hours at a temperature of 70-120 ℃, and sieving with a 120-mesh sieve after grinding to obtain a raw material mixture;
s3, presintering: heating the raw material mixture obtained in the step S2 from normal temperature to 850-950 ℃ at a heating rate of 3-5 ℃/min, presintering at a constant temperature for 2-4 hours, naturally cooling to the room temperature, and grinding to obtain presintering powder;
s4, secondary ball milling: adding agate balls and absolute ethyl alcohol into the pre-sintered powder obtained in the step S3, ball milling for 6-10 hours, separating the agate balls, drying for 10-24 hours at the temperature of 70-120 ℃, grinding, and sieving with a 180-mesh sieve to obtain ball-milled pre-sintered powder;
s5, tabletting, namely adding 6% polyvinyl alcohol aqueous solution into the ball-milled pre-sintered powder obtained in the step S4, granulating, sieving with a 40-mesh sieve to obtain a quicksand-shaped spherical powder substance, and maintaining the pressure for 10S to 60S under the unidirectional pressure condition of 100MPa to 200MPa to obtain a disc-shaped ceramic blank;
s6, glue discharging: raising the temperature of the wafer-shaped ceramic blank obtained in the step S5 to 500-600 ℃ at a heating rate of 1-3 ℃/min, preserving heat for 1-3 h, and naturally cooling to room temperature to obtain a wafer-shaped ceramic blank after glue discharge;
s7, sintering: sintering the disc-shaped ceramic blank body with the adhesive discharged obtained in the step S5 to obtain a sintered ceramic blank body; the sintering conditions are as follows: firstly, heating from room temperature to 1160-1220 ℃ at a heating rate of 3-5 ℃/min, sintering at constant temperature for 2-3 h, and then cooling to room temperature at a cooling rate of 5 ℃/min;
s8, polishing: polishing the upper and lower surfaces of the sintered ceramic blank obtained in the step S7 by using 600-mesh sand paper, polishing the upper and lower surfaces by using 2000-mesh sand paper and silicon carbide to a thickness of 0.3-0.5 mm, putting the ceramic blank into deionized water, ultrasonically cleaning the ceramic blank, and drying the ceramic blank to obtain a polished ceramic blank;
s9, surface metallization: and (3) uniformly coating silver paste with the thickness of 0.01-0.03 mm on the upper and lower surfaces of the polished ceramic blank obtained in the step (S8), then placing the ceramic blank in a resistance furnace, heating to the temperature of 850 ℃ at the heating rate of 3-6 ℃/min, preserving heat for 10min, and naturally cooling to the room temperature to obtain the sodium bismuth titanate-based high-entropy medium energy storage ceramic material.
3. The method according to claim 2, wherein the premix, agate balls and absolute ethanol in S2 are used in a ratio of 0.30g to 1g:0.45mL.
4. The method according to claim 2, wherein the pre-sintered powder, agate balls and absolute ethanol in S4 are used in a ratio of 0.28g to 1g:0.40mL.
5. The method according to claim 2, wherein the mass ratio of the 6% polyvinyl alcohol aqueous solution to the pre-sintered powder after ball milling in S5 is (5% -10%): 1.
6. the method according to claim 2, wherein the time of the ultrasonic cleaning in S8 is 10min to 20min.
7. Use of a sodium bismuth titanate based high entropy medium energy storage ceramic material prepared by a method according to any one of claims 2-6, characterized in that the sodium bismuth titanate based high entropy medium energy storage ceramic material is used for the preparation of pulse capacitors.
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| CN115536390A (en) * | 2022-10-12 | 2022-12-30 | 长安大学 | Transparent dielectric energy storage ceramic material and preparation method and application thereof |
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| CN115991599A (en) * | 2021-10-20 | 2023-04-21 | 深圳先进电子材料国际创新研究院 | High-entropy perovskite oxide doped ceramic, preparation method and application thereof |
| CN115536390A (en) * | 2022-10-12 | 2022-12-30 | 长安大学 | Transparent dielectric energy storage ceramic material and preparation method and application thereof |
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