CN110600266A - Preparation method of BCZT energy storage ceramic material with adjustable Curie temperature - Google Patents
Preparation method of BCZT energy storage ceramic material with adjustable Curie temperature Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 68
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000001723 curing Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 60
- 239000011259 mixed solution Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 24
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000003990 capacitor Substances 0.000 claims description 11
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- 230000005684 electric field Effects 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 230000010287 polarization Effects 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention discloses a preparation method of a BCZT energy storage ceramic material with adjustable Curie temperature, which comprises the following steps: preparation of Metal ion ratio and Ba0.85Ca0.15Zr0.1Ti0.9O31.25:1, adjusting the pH value, and heating to obtain sol; drying the sol in a blast drying oven, and grinding into powder; placing the prepared powder in a muffle furnace to calcine the powder into BCZT oxide powder; grinding, granulating and molding BCZT oxide powder, and sintering in a muffle furnace; and finally, coating silver slurry on two surfaces of the ceramic material obtained by sintering, and sintering and curing at a certain temperature to form the metal silver electrode. The invention adopts a sol-gel method to prepare Ba0.85Ca0.15Zr0.1Ti0.9O3The ceramic material effectively regulates and controls the Curie temperature of the BCZT ferroelectric ceramic material to be close to the room temperature, and has the advantages of simple process, low cost, high energy storage density, high energy storage efficiency and the like.
Description
Technical Field
The invention belongs to the technical field of electronic materials and devices, and particularly relates to a preparation method of a BCZT energy storage ceramic material with adjustable Curie temperature.
Background
With the rapid development of energy storage technology, dielectric capacitors have received much attention due to their ultra-high power density. The energy storage dielectric capacitor can be applied to occasions needing larger power output, such as tanks, electromagnetic guns, directional energy weapons, electrified launching platforms and the like, all of the facilities need working current of more than 100kA, and common energy devices are difficult to meet the requirement. The dielectric capacitor has the limitations that the energy storage density and the energy storage efficiency are low, which is not beneficial to the miniaturization and the light weight of the energy storage element, and the stability of the nonlinear dielectric material near the phase transition temperature is poor, which restricts the application range of the dielectric capacitor. The key problem in achieving the application of energy storage dielectric capacitors is to achieve higher energy storage density and better stability, and the solution of the problem will bring a major breakthrough to the technical field of related energy sources.
The ferroelectric material is used as a nonlinear dielectric, and the storage density can be calculated by a formula (the electric displacement D of the ferroelectric with higher dielectric constant can be regarded as equal to the electric polarization strength P)Therefore, the energy storage density of the energy storage element is related to the breakdown field strength and the saturation polarization value, and the energy storage efficiency is related to the energy dissipation in the charging and discharging process. Therefore, how to reduce the residual polarization value of the material through different ways while keeping the higher saturation polarization value of the material and improve the breakdown field strength of the ceramic becomes a hotspot of the research on the energy storage dielectric ceramic. In recent years, researchers have focused on perovskite-type Ba0.85Ca0.15Zr0.1Ti0.9O3(BCZT) ferroelectric ceramic material was systematically studied. Researches show that the Curie temperature of the BCZT ceramic material is about 120 ℃, excellent piezoelectric property, higher dielectric constant and very low dielectric loss are obtained at room temperature, and the BCZT ceramic material is obtained at room temperatureP-EThe ferroelectric hysteresis loop has a larger remanent polarization value (~ 12 mu C/cm)2). If the high energy storage density and the high energy storage efficiency near the room temperature are required to be realized, the Curie temperature of the BCZT can be regulated and controlled.
Disclosure of Invention
The invention solves the technical problem of providing an economical and practical preparation method of the BCZT energy storage ceramic material with adjustable Curie temperature, which has simple process and does not need complex post-treatment steps.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the BCZT energy storage ceramic material with adjustable Curie temperature is characterized by comprising the following specific steps:
step S1: with Ba (NO)3)2、Ca(NO3)2·4H2O、ZrOCl2·8H2O, tetrabutyl titanate, ammonia water and citric acid are used as initial raw materials, wherein the raw materials are Ba0.85Ca0.15Zr0.1Ti0.9O3Respectively weighing raw material Ba (NO)3)2、Ca(NO3)2·4H2O、ZrOCl2·8H2O and tetrabutyl titanate;
step S2: respectively dissolving tetrabutyl titanate and citric acid in 10mL and 30mL of ethanol, respectively stirring until the tetrabutyl titanate and the citric acid are completely dissolved, and then dripping the ethanol solution of tetrabutyl titanate into the ethanol solution of citric acid to obtain a mixed solution A;
step S3: zr (NO)3)4·5H2O、Ca(NO3)2·4H2O and Ba (NO)3)2Dissolving in 30mL of deionized water, heating and stirring until the mixture is completely dissolved to obtain a mixed solution B;
step S4: dropwise adding the mixed solution B obtained in the step S3 into the mixed solution A obtained in the step S2 to obtain a mixed solution C, dropwise adding ammonia water to adjust the pH value of the mixed solution C to 5-9, and continuously stirring at 80 ℃ to obtain a clear transparent solution;
step S5: stirring the clear transparent solution obtained in the step S4 in a water bath at 80 ℃ for 4 hours, and then increasing the viscosity of the solution to finally form yellow transparent sol;
step S6: drying the yellow transparent gel obtained in the step S5 in a forced air drying oven at 150 ℃ for 24h, and then uniformly grinding to obtain black powder;
step S7: putting the black powder obtained in the step S6 into a muffle furnace, heating to 1000 ℃ at the heating rate of 5 ℃/min, and calcining for 4h to obtain Ba0.85Ca0.15Zr0.1Ti0.9O3Oxide powder;
step S8: ba obtained in step S70.85Ca0.15Zr0.1Ti0.9O3Adding 3wt% of PVA into oxide powder, grinding and granulating, molding under 200MPa, heating to 1300 ℃ at a heating rate of 5 ℃/min in a muffle furnace, and sintering for 2h to obtain Ba0.85Ca0.15Zr0.1Ti0.9O3An oxide ceramic material;
step S9: ba obtained in step S80.85Ca0.15Zr0.1Ti0.9O3Coating silver slurry on the oxide ceramic material, sintering at 600 ℃ for 20min, and curing to form a metal silver electrode, wherein the Ba is Ba0.85Ca0.15Zr0.1Ti0.9O3The oxide ceramic material has high dielectric constant, energy storage density and energy storage efficiency, and can be used as an energy storage capacitor material.
More preferably, the tetrabutyl titanate is stirred for 15min at a rotation speed of 300 rpm while being dropwise added to the ethanol in step S2, and the molar ratio of the citric acid to the metal cation in the mixed solution a is 1.25: 1.
More preferably, Ba is produced by adjusting the pH of the mixed solution C to 9 with aqueous ammonia in step S40.85Ca0.15Zr0.1Ti0.9O3The Curie temperature of the oxide ceramic material is regulated to 4 ℃, and the energy storage density is 1.07J/cm under a test electric field of 185kV/cm3The energy storage efficiency is 91.2%, and the high energy storage density and energy storage efficiency are obtained at room temperature due to the fact that the Curie temperature is regulated to be close to the room temperature, and the energy storage capacitor material can be used as an energy storage capacitor material at room temperature.
Compared with the prior art, the invention ensures that Ba is enabled by adjusting the pH value of the solution0.85Ca0.15Zr0.1Ti0.9O3The Curie temperature of the ferroelectric ceramic material is reduced, and when the pH value of the solution is adjusted to 9 by ammonia water, the finally prepared Ba0.85Ca0.15Zr0.1Ti0.9O3The dielectric constant of the ferroelectric ceramic material reaches the optimal value, the dielectric constant is 2500 at 100Hz room temperature, and the energy storage density reaches the optimal value of 1.1J/cm3And the energy storage density reaches an optimal value of 91%. The invention also has the following advantages and beneficial effects:
1. the invention can effectively reduce Ba by optimizing the pH value of the solution0.85Ca0.15Zr0.1Ti0.9O3Curie temperature of the ceramic material, thereby refiningP-EThe electric hysteresis loop and the breakdown-resistant field strength are kept at a higher level, so that the energy storage density and the energy storage efficiency of the BCZT ceramic material are improved.
2. The preparation method is simple, does not need complex post-treatment steps, is economical and practical, and adopts the sol-gel method to prepare the Ba0.85Ca0.15Zr0.1Ti0.9O3The ceramic material effectively reduces the Curie temperature of the BCZT ferroelectric ceramic material, and has the advantages of simple process, low cost, high energy storage density, high energy storage efficiency and the like.
Drawings
FIG. 1 is an XRD pattern of BCZT ceramic materials prepared in example 1 and example 2;
FIG. 2 shows the dielectric properties of BCZT ceramic materials prepared in examples 1 and 2;
fig. 3 is a leakage current of the BCZT ceramic materials prepared in examples 1 and 2;
FIG. 4 is a dielectric thermogram of BCZT ceramic material prepared in example 1 and example 2;
FIG. 5 is the room temperature of the BCZT ceramic materials prepared in examples 1 and 2P-EAn electric hysteresis loop;
fig. 6 is a graph of energy storage density and energy storage efficiency of the BCZT ceramic materials prepared in examples 1 and 2.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Step S1: with a purity of more than 99.99% of Ba (NO)3)2、Ca(NO3)2·4H2O、ZrOCl2·8H2O, tetrabutyl titanate, ammonia water and citric acid are used as initial raw materials, wherein the raw materials are Ba0.85Ca0.15Zr0.1Ti0.9O3Respectively weighing raw material Ba (NO)3)2、Ca(NO3)2·4H2O、ZrOCl2·8H2O and tetrabutyl titanate;
step S2: respectively dissolving tetrabutyl titanate and citric acid in 10mL and 30mL of ethanol, stirring the solutions respectively until the tetrabutyl titanate and the citric acid are completely dissolved, and then dripping the ethanol solution of tetrabutyl titanate into the ethanol solution of citric acid to obtain a mixed solution A, wherein the molar ratio of the citric acid to the metal cations in the mixed solution A is 1.25: 1;
step S3: zr (NO)3)4·5H2O、Ca(NO3)2·4H2O and Ba (NO)3)2Dissolving in 30mL deionized water, heating to 80 deg.C, and stirring to completeDissolving to obtain a mixed solution B;
step S4: dropwise adding the mixed solution B obtained in the step S3 into the mixed solution A obtained in the step S2 to obtain a mixed solution C, dropwise adding ammonia water to adjust the pH value of the mixed solution C to 6, and continuously stirring at 80 ℃ to obtain a clear transparent solution;
step S5: stirring the clear transparent solution obtained in the step S4 in a water bath at 80 ℃ for 4 hours, and then increasing the viscosity of the solution to finally form yellow transparent sol;
step S6: drying the yellow transparent gel obtained in the step S5 in a forced air drying oven at 150 ℃ for 24h, and then uniformly grinding to obtain black powder;
step S7: putting the black powder obtained in the step S6 into a muffle furnace, heating to 1000 ℃ at the heating rate of 5 ℃/min, and calcining for 4h to obtain Ba0.85Ca0.15Zr0.1Ti0.9O3Oxide powder;
step S8: ba obtained in step S70.85Ca0.15Zr0.1Ti0.9O3Adding 3wt% of PVA into oxide powder, grinding and granulating, molding under 200MPa, heating to 1300 ℃ at a heating rate of 5 ℃/min in a muffle furnace, and sintering for 2h to obtain Ba0.85Ca0.15Zr0.1Ti0.9O3Oxide (BCZT) ceramic material;
step S9: ba obtained in step S80.85Ca0.15Zr0.1Ti0.9O3And coating the silver paste on the oxide ceramic material, sintering at 600 ℃ for 20min, and curing to form the metal silver electrode.
Example 2
Step S1: with Ba (NO)3)2、Ca(NO3)2·4H2O、ZrOCl2·8H2O, tetrabutyl titanate, ammonia water and citric acid are used as initial raw materials, wherein the raw materials are Ba0.85Ca0.15Zr0.1Ti0.9O3Respectively weighing raw material Ba (NO)3)2、Ca(NO3)2·4H2O、ZrOCl2·8H2O and tetrabutyl titanate;
step S2: respectively dissolving tetrabutyl titanate and citric acid in 10mL and 30mL of ethanol, stirring the solutions respectively until the tetrabutyl titanate and the citric acid are completely dissolved, and then dripping the ethanol solution of tetrabutyl titanate into the ethanol solution of citric acid to obtain a mixed solution A, wherein the molar ratio of the citric acid to the metal cations in the mixed solution A is 1.25: 1;
step S3: zr (NO)3)4·5H2O、Ca(NO3)2·4H2O and Ba (NO)3)2Dissolving in deionized water, heating and stirring until the mixture is completely dissolved to obtain a mixed solution B;
step S4: dropwise adding the mixed solution B obtained in the step S3 into the mixed solution A obtained in the step S2 to obtain a mixed solution C, dropwise adding ammonia water to adjust the pH value of the mixed solution C to 9, and continuously stirring at 80 ℃ to obtain a clear transparent solution;
step S5: stirring the clear transparent solution obtained in the step S4 in a water bath at 80 ℃ for 4 hours, and then increasing the viscosity of the solution to finally form yellow transparent sol;
step S6: drying the yellow transparent gel obtained in the step S5 in a forced air drying oven at 150 ℃ for 24h, and then uniformly grinding to obtain black powder;
step S7: putting the black powder obtained in the step S6 into a muffle furnace, heating to 1000 ℃ at the heating rate of 5 ℃/min, and calcining for 4h to obtain Ba0.85Ca0.15Zr0.1Ti0.9O3Oxide powder;
step S8: ba obtained in step S70.85Ca0.15Zr0.1Ti0.9O3Adding 3wt% of PVA into oxide powder, grinding and granulating, molding under 200MPa, heating to 1300 ℃ at a heating rate of 5 ℃/min in a muffle furnace, and sintering for 2h to obtain Ba0.85Ca0.15Zr0.1Ti0.9O3Oxide (BCZT) ceramic material;
step S9: ba obtained in step S80.85Ca0.15Zr0.1Ti0.9O3And coating the silver paste on the oxide ceramic material, sintering at 600 ℃ for 20min, and curing to form the metal silver electrode.
Fig. 1 is an XRD pattern of the BCZT ceramic materials prepared in example 1 and example 2, showing the effect of different pH values on the phase structure.
Fig. 2 shows the room temperature dielectric properties of the BCZT ceramic materials prepared in example 1 and example 2, compared to example 2, which achieves higher dielectric constant and smaller dielectric loss.
Fig. 3 shows the room temperature leakage current of the BCZT ceramic materials prepared in examples 1 and 2, and it can be seen from the figure that the leakage current of the BCZT ceramic material prepared in example 2 is smaller than that of the BCZT ceramic material prepared in example 1, and the insulation of the BCZT ceramic material prepared in example 2 is better as seen from the dielectric test results in fig. 2.
Fig. 4 is a dielectric thermogram of the BCZT ceramic materials prepared in examples 1 and 2, and it can be seen from the graph that the curie temperature of the BCZT ceramic materials prepared in examples 1 to 2 is decreased from 118 ℃ to 4 ℃ with the increase of pH, so that the curie temperature of the BCZT ceramic material prepared in example 2 is controlled to be around room temperature.
FIG. 5 is a BCZT ceramic material prepared in example 1 and example 2P-EHysteresis loop as can be seen from the figure, the BCZT ceramic materials prepared in example 1 and example 2 all showed hysteresis loops and current peaks of conventional ferroelectrics at a test frequency of 10Hz and under different test electric fields. Under the same test electric field, the BCZT ceramic material prepared in example 2 has a higher saturation polarization value, a lower remanent polarization value and an extremely low coercive field strength. According to the calculation formula of the energy storage density of the nonlinear dielectric medium, the energy storage density U of the BCZT ceramic material prepared in example 1 is 0.47J/cm when the test electric field E is 160kV/cm3The energy storage efficiency eta is 37.8 percent, and the BCZT ceramic material prepared in the example 2 obtains the energy storage density of 1.07J/cm under the test electric field of 185kV/cm3The energy storage efficiency was 91.2%. The dielectric temperature spectrum test result shown in fig. 4 shows that the BCZT ceramic material prepared in example 2 has higher energy storage density and energy storage efficiency because the curie temperature of the BCZT ceramic material is controlled to be near room temperature.
Fig. 6 is a graph of energy storage density and energy storage efficiency of the BCZT ceramic materials prepared in examples 1 and 2, and the energy storage density of the BCZT ceramic materials prepared in examples 1 and 2 gradually increases with the increase of the electric field. The energy storage density and the energy storage efficiency of the BCZT ceramic material prepared in example 2 are remarkably increased by adjusting the pH value, the energy storage density of the BCZT ceramic material prepared in example 2 is about 2 times that of example 1 under the same electric field, and the energy storage efficiencies of the BCZT ceramic materials prepared in example 1 and example 2 are respectively 30% and 91.2% under the maximum test electric field. The energy storage efficiency of the BCZT ceramic material is improved by about 3 times by regulating and controlling the pH value.
In summary, the curie temperature of the BCZT ceramic material obtained by the method of the present invention can be controlled to be near the room temperature, and the BCZT ceramic material prepared in example 2 has a higher energy storage density and a high energy storage efficiency at the room temperature, and is beneficial to the application of the BCZT ceramic material in the aspect of energy storage at the room temperature.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (3)
1. A preparation method of a BCZT energy storage ceramic material with adjustable Curie temperature is characterized by comprising the following specific steps:
step S1: with Ba (NO)3)2、Ca(NO3)2·4H2O、ZrOCl2·8H2O, tetrabutyl titanate, ammonia water and citric acid are used as initial raw materials, wherein the raw materials are Ba0.85Ca0.15Zr0.1Ti0.9O3Respectively weighing raw material Ba (NO)3)2、Ca(NO3)2·4H2O、ZrOCl2·8H2O and tetrabutyl titanate;
step S2: respectively dissolving tetrabutyl titanate and citric acid in 10mL and 30mL of ethanol, respectively stirring until the tetrabutyl titanate and the citric acid are completely dissolved, and then dripping the ethanol solution of tetrabutyl titanate into the ethanol solution of citric acid to obtain a mixed solution A;
step S3: zr (NO)3)4·5H2O、Ca(NO3)2·4H2O and Ba (NO)3)2Dissolving in 30mL of deionized water, heating and stirring until the mixture is completely dissolved to obtain a mixed solution B;
step S4: dropwise adding the mixed solution B obtained in the step S3 into the mixed solution A obtained in the step S2 to obtain a mixed solution C, dropwise adding ammonia water to adjust the pH value of the mixed solution C to 5-9, and continuously stirring at 80 ℃ to obtain a clear transparent solution;
step S5: stirring the clear transparent solution obtained in the step S4 in a water bath at 80 ℃ for 4 hours, and then increasing the viscosity of the solution to finally form yellow transparent sol;
step S6: drying the yellow transparent gel obtained in the step S5 in a forced air drying oven at 150 ℃ for 24h, and then uniformly grinding to obtain black powder;
step S7: putting the black powder obtained in the step S6 into a muffle furnace, heating to 1000 ℃ at the heating rate of 5 ℃/min, and calcining for 4h to obtain Ba0.85Ca0.15Zr0.1Ti0.9O3Oxide powder;
step S8: ba obtained in step S70.85Ca0.15Zr0.1Ti0.9O3Adding 3wt% of PVA into oxide powder, grinding and granulating, molding under 200MPa, heating to 1300 ℃ at a heating rate of 5 ℃/min in a muffle furnace, and sintering for 2h to obtain Ba0.85Ca0.15Zr0.1Ti0.9O3An oxide ceramic material;
step S9: ba obtained in step S80.85Ca0.15Zr0.1Ti0.9O3Coating silver slurry on the oxide ceramic material, sintering at 600 ℃ for 20min, and curing to form a metal silver electrode, wherein the Ba is Ba0.85Ca0.15Zr0.1Ti0.9O3The oxide ceramic material has high dielectric constant, energy storage density and energy storage efficiency, and can be used as an energy storage capacitor material.
2. The method for preparing a BCZT energy storage ceramic material with adjustable Curie temperature according to claim 1, wherein: and in the step S2, stirring the tetrabutyl titanate for 15min at the rotating speed of 300 revolutions per minute when the tetrabutyl titanate is dropwise added into the ethanol, wherein the molar ratio of the citric acid to the metal cations in the mixed solution A is 1.25: 1.
3. The method for preparing a BCZT energy storage ceramic material with adjustable Curie temperature according to claim 2, wherein: in step S4, when the pH value of the mixed solution C is adjusted to 9 by ammonia water, Ba is prepared0.85Ca0.15Zr0.1Ti0.9O3The Curie temperature of the oxide ceramic material is regulated to 4 ℃, and the energy storage density is 1.07J/cm under a test electric field of 185kV/cm3The energy storage efficiency is 91.2%, and the high energy storage density and energy storage efficiency are obtained at room temperature due to the fact that the Curie temperature is regulated to be close to the room temperature, and the energy storage capacitor material can be used as an energy storage capacitor material at room temperature.
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