CN116874295A - Layered ceramic medium with high energy storage density and high energy storage efficiency and preparation method thereof - Google Patents
Layered ceramic medium with high energy storage density and high energy storage efficiency and preparation method thereof Download PDFInfo
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- CN116874295A CN116874295A CN202310670794.1A CN202310670794A CN116874295A CN 116874295 A CN116874295 A CN 116874295A CN 202310670794 A CN202310670794 A CN 202310670794A CN 116874295 A CN116874295 A CN 116874295A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 149
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 48
- 229910002367 SrTiO Inorganic materials 0.000 claims abstract description 12
- 238000010030 laminating Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 50
- 238000000498 ball milling Methods 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 41
- 239000000843 powder Substances 0.000 claims description 32
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 22
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- 230000010287 polarization Effects 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 17
- 238000005266 casting Methods 0.000 claims description 13
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
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- 238000010345 tape casting Methods 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
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- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 8
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a layered ceramic medium with high energy storage density and high energy storage efficiency and a preparation method thereof, wherein the ceramic medium is of a layered structure formed by alternately laminating a first medium layer and a second medium layer, the first medium layer is a high-polarization-intensity medium layer, and the material comprises (1-x-y) BiFeO 3 ‑xBaTiO 3 ‑yBa(Zn 1/2 Ta 2/3 )O 3 And Bi (Bi) 0.39 Na 0.36 Sr 0.25 TiO 3 Wherein x=0.30-0.40 and y=0.05-0.15; the second dielectric layer is a dielectric layer with high compressive strength and high energy storage efficiency, and the material comprises (1-z) SrTiO 3 ‑zBiFeO 3 And BaBi 2 Nb 2 O 9 Which is provided withMedium z=0.25-0.35; the thickness of the layered structure is at least 25 μm. The preparation method can obtain the ceramic medium with high energy storage density and high energy storage efficiency.
Description
Technical Field
The invention belongs to the technical field of energy storage ceramic media, and particularly relates to a layered ceramic medium with high energy storage density and high energy storage efficiency and a preparation method thereof.
Background
With the increasing demand for non-renewable energy sources such as coal, oil, etc., there is a need to develop clean renewable energy sources and efficient energy storage and conversion technologies. Batteries, electrochemical capacitors and dielectric capacitors are currently the main types of electric energy storage devices, and in contrast, dielectric capacitors have the characteristics of high power density, high charge and discharge speed, safety, reliability and the like, and play an important role in pulse systems of laser weapons, electromagnetic transmitters, hybrid electric vehicles and other devices. Thin film dielectric capacitors, polymer-based thick film dielectric capacitors, and bulk ceramic dielectric capacitors can be broadly classified according to the type and thickness of dielectric material used for the dielectric capacitors. While polymers and thin film dielectrics can withstand higher electric field strengths due to their thinner thickness, thinner thickness limits the increase in total energy density. The ceramic dielectric is easy to prepare into a multilayer ceramic capacitor, and the preparation technology is mature, so that the energy storage ceramic capacitor is widely paid attention to in recent years.
In general, the energy storage performance of a ceramic dielectric can be calculated from measured hysteresis loops, the area enclosed by the hysteresis loops being expressed as the energy loss density (W loss ) And releasable energy storage density (W rec ) And energy storage efficiency (η) is calculated using the following formula:
η＝W rec /(W rec +W loss )×100％ (2)
wherein P is max 、P r P and E represent maximum polarization, remnant polarization, polarization and electric field strength, respectively. Based on the above formula, it can be seen that a large P max Small P r And high compressive strength are key to achieving high energy storage performance. In many ceramic systems, antiferroelectric materials exhibit a large P due to their unique dual hysteresis loop characteristics max Negligible P r And moderate compressive strength, and high energy storage performance is easy to obtain. However, most high-performance antiferroelectric ceramics have heavy metal Pb elements, which is not beneficial to environmental protection and health and safety of human bodies. Up to now, lead-free ceramic media are difficult to obtain synchronous change due to maximum polarization, remnant polarization and compressive strengthAs a result, the energy storage performance of the lead-based antiferroelectric ceramic material is greatly different from that of the lead-based antiferroelectric ceramic material, and the energy storage density and the energy storage efficiency of the lead-free ceramic medium are greatly improved.
The preparation method of the lead-free energy storage ceramic medium reported at present mainly adopts the traditional granulation and unidirectional compression molding process, the ceramic material prepared by the method is generally thicker (> 500 mu m), and the electrical property test and the energy storage property calculation are carried out after the ceramic material is polished to 100-200 mu m, so that the preparation cost and the preparation period are necessarily increased; and it is difficult to directly obtain a high-quality thin ceramic sample having a thickness of less than 100 μm. Although the casting molding process is easy to prepare high-quality thin-layer ceramic media, the research of the layered energy storage ceramic is very slow due to factors such as sintering matching property and the like, and the research is mainly focused on the layered structure design of similar constituent materials, so that the energy storage density and the energy storage efficiency of the lead-free energy storage ceramic are difficult to be greatly improved all the time.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a layered ceramic medium with high energy storage density and high energy storage efficiency and a preparation method thereof. The technical problems to be solved by the invention are realized by the following technical scheme:
the first aspect of the present invention provides a layered high energy storage density and high energy storage efficiency ceramic dielectric, the layered high energy storage density and high energy storage efficiency ceramic dielectric is a layered structure formed by alternately stacking a first dielectric layer and a second dielectric layer, the first dielectric layer is a high polarization strength dielectric layer, and the material of the high polarization strength dielectric layer comprises (1-x-y) BiFeO 3 -xBaTiO 3 -yBa(Zn 1/2 Ta 2/3 )O 3 And Bi (Bi) 0.39 Na 0.36 Sr 0.25 TiO 3 Wherein x=0.30-0.40 and y=0.05-0.15; the second dielectric layer is a dielectric layer with high compressive strength and high energy storage efficiency, and the material of the dielectric layer with high compressive strength and high energy storage efficiency comprises (1-z) SrTiO 3 -zBiFeO 3 And BaBi 2 Nb 2 O 9 Wherein z=0.25-0.35; the thickness of the layered structure is at least 25 μm.
The second aspect of the invention provides a method for preparing a layered ceramic medium with high energy storage density and high energy storage efficiency, comprising the steps of:
respectively weighing corresponding oxides or carbonates according to chemical formulas of the first material and the second material to obtain a first raw material and a second raw material, wherein the first material has high polarization strength, and the second material has high compressive strength and high energy storage efficiency;
respectively performing first ball milling on the first raw material and the second raw material for 4-24 hours; drying at 80-100deg.C;
calcining the raw materials subjected to ball milling and drying for 2-4 hours at 800-900 ℃ respectively to obtain a pre-synthesized phase composition;
respectively performing secondary ball milling on the pre-synthesized phase composition for 4-24 hours;
drying and sieving the raw materials subjected to the second ball milling at 80-100 ℃ respectively to obtain ceramic powder;
firstly mixing a first organic solution for 4-6 hours, then adding a second organic solution, a binder and the ceramic powder into the first organic solution, and mixing again for 4-6 hours to obtain a first ceramic slurry and a second ceramic slurry for tape casting;
preparing the first ceramic slurry and the second ceramic slurry into a high-polarization-strength film, a high-compressive strength film and a high-energy-storage-efficiency film through tape casting and forming processes respectively; wherein the height of the scraper in the casting forming process is 80-200 mu m;
cutting, laminating, pressing and other processes are carried out on the high-polarization-strength film, the high-compressive-strength film and the high-energy-storage-efficiency film to obtain ceramic green bodies with different layered structures;
and (3) carrying out glue discharging treatment on the ceramic green body at 550-600 ℃, wherein the heat preservation time is 8-10h, and then sintering the ceramic green body subjected to glue discharging under a closed condition, so as to finally obtain the layered ceramic medium with high energy storage density and high energy storage efficiency.
Preferably, the first feedstock comprises (1-x-y) BiFeO 3 -xBaTiO 3 -yBa(Zn 1/2 Ta 2/3 )O 3 And Bi (Bi) 0.39 Na 0.36 Sr 0.25 TiO 3 Wherein x=0.30-0.40 and y=0.05-0.15, and the second raw material comprises (1-z) SrTiO 3 -zBiFeO 3 And BaBi 2 Nb 2 O 9 Wherein z=0.25-0.35.
Preferably, the (1-x-y) BiFeO 3 -xBaTiO 3 -yBa(Zn 1/2 Ta 2/3 )O 3 The corresponding oxide or carbonate comprises Bi 2 O 3 、Fe 2 O 3 、BaCO 3 、TiO 2 ZnO and Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the The Bi is 0.39 Na 0.36 Sr 0.25 TiO 3 The corresponding oxide or carbonate comprises Bi 2 O 3 、Na 2 CO 3 、SrCO 3 And TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The (1-z) SrTiO 3 -zBiFeO 3 The corresponding oxide or carbonate comprises SrCO 3 、TiO 2 、Bi 2 O 3 And Fe (Fe) 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The BaBi 2 Nb 2 O 9 The corresponding oxide or carbonate comprises BaCO 3 、Bi 2 O 3 And Nb (Nb) 2 O 5 。
Preferably, the first organic solution is a mixed solution of absolute ethyl alcohol, butanone and triolein, and the mass ratio of the absolute ethyl alcohol, the butanone and the triolein is as follows: 40-60:80-120:3-6.
Preferably, the addition amount of butanone in the first type of organic solution is 80-100% of the mass of the ceramic powder.
Preferably, the second type of organic solution is a mixed solution of dibutyl phthalate and polyethylene glycol, and the mass ratio of dibutyl phthalate to polyethylene glycol is 1:1.
Preferably, the addition amount of dibutyl phthalate and polyethylene glycol in the second type of organic solution is 2-5% of the mass of the ceramic powder.
Preferably, the addition amount of the binder is 8% -15% of the mass of the ceramic powder.
Preferably, the first type of organic solution is mixed by a ball milling process, and the ball milling medium comprises zirconia balls, wherein the adding amount of the zirconia balls is 1.5-2.5 times of the mass of the ceramic powder.
Compared with the prior art, the invention has the beneficial effects that:
the layered ceramic medium with high energy storage density and high energy storage efficiency and the preparation method thereof are formed by alternately laminating the high-polarization-intensity dielectric layers, the high-compressive strength dielectric layers and the high-energy storage efficiency dielectric layers of different materials, can integrate the excellent performances of the two different materials, not only improves the energy storage density of the lead-free ceramic, but also can promote the energy storage efficiency to be greatly improved, and further obtains excellent comprehensive performance. Meanwhile, by adopting the preparation method, the problem of heterogeneous ceramic sintering matching can be effectively solved, the problem that the energy storage density and the energy storage efficiency of the existing lead-free energy storage ceramic medium are difficult to synergistically enhance can be solved, and the ceramic medium with high energy storage density and high energy storage efficiency can be obtained.
Drawings
FIG. 1 is a schematic diagram of a layered high energy storage density and high energy storage efficiency ceramic media provided by the present invention;
FIG. 2 is a schematic structural view of another layered high energy storage density and high energy storage efficiency ceramic media provided by the present invention;
FIG. 3 is a schematic structural view of yet another layered high energy storage density and high energy storage efficiency ceramic media provided by the present invention;
FIG. 4 is a schematic structural diagram of a layered high energy storage density and high energy storage efficiency ceramic media prepared in accordance with an embodiment of the present invention;
FIG. 5 is a graph showing the results of a hysteresis loop test of layered high energy storage density and high energy storage efficiency ceramic media prepared in accordance with the first embodiment of the present invention;
FIG. 6 is a schematic structural diagram of a layered high energy storage density and high energy storage efficiency ceramic media prepared in accordance with example two of the present invention;
FIG. 7 is a graph showing the results of the hysteresis loop test of layered high energy storage density and high energy storage efficiency ceramic media prepared in example two of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto.
The current method for improving the energy storage performance of the lead-free ceramic medium is mainly focused on the aspects of element doping, grain size and domain structure regulation, core-shell structure construction and the like. Although the layered structure has been paid attention to in recent years to improve the energy storage performance of lead-free ceramic dielectrics, the related research is slow due to factors such as sintering matching property, and commonly used base materials of different dielectric layers are of the same composition, for example, yuan et al of the Western-style transportation university adopts a chemical coating method to obtain BaTiO with a core-shell structure 3 @SiO 2 Powder, then design and prepare BaTiO 3 And BaTiO 3 @SiO 2 Layered ceramic material composed of dielectric layers, 1.80J/cm was obtained 3 And 71.5% energy storage efficiency. Li et al, university of Huazhong technology, uses 0.65Bi with high polarization intensity 0.5 Na 0.5 TiO 3 -0.35SrTiO 3 And 0.45Bi with high energy storage efficiency 0.5 Na 0.5 TiO 3 -0.55Sr 0.7 Bi 0.2 TiO 3 The dielectric material is designed into a layered structure, the influence of the number of interfaces on the breakdown behavior and polarization characteristics of layered ceramics is researched, and finally 4.48J/cm is obtained 3 The effective energy storage density and the energy storage efficiency of about 90 percent. Although the research improves the energy storage density and the energy storage efficiency of the lead-free ceramic medium to a certain extent, the matrix materials of the two layers of medium materials are the same, the complementation of the excellent performances of the ceramic medium with large material composition difference can not be realized, and the energy storage density and the energy storage efficiency are still difficult to be improved greatly.
Based on the method, the invention provides the layered ceramic medium with high energy storage density and high energy storage efficiency and the preparation method thereof, which better overcome the defects that the energy storage density and the energy storage efficiency of the existing lead-free energy storage ceramic medium are difficult to be synergistically enhanced, the sintering matching property of layered heterogeneous ceramic is poor, and the like, and further improve the development efficiency of the lead-free ceramic medium with the energy storage characteristic.
The first aspect of the present invention discloses a layered ceramic dielectric with high energy storage density and high energy storage efficiency, please refer to fig. 1, fig. 1 is a layered structure formed by alternately stacking a first dielectric layer 1 and a second dielectric layer 2, the first dielectric layer 1 is a high-polarization-strength dielectric layer, and the material of the high-polarization-strength dielectric layer comprises (1-x-y) BiFeO 3 -xBaTiO 3 -yBa(Zn 1/2 Ta 2/3 )O 3 And Bi (Bi) 0.39 Na 0.36 Sr 0.25 TiO 3 Wherein x=0.30-0.40 and y=0.05-0.15; the second dielectric layer 2 is a dielectric layer with high compressive strength and high energy storage efficiency, and the material of the dielectric layer with high compressive strength and high energy storage efficiency comprises (1-z) SrTiO 3 -zBiFeO 3 And BaBi 2 Nb 2 O 9 Wherein z=0.25-0.35; the thickness of the layered structure is at least 25 μm.
That is, the layered high energy storage density and high energy storage efficiency ceramic medium of the present invention may have a layered structure of any one of the high polarization strength dielectric layers and any one of the high compressive strength and high energy storage efficiency dielectric layers, such as (1-x-y) BiFeO 3 -xBaTiO 3 -yBa(Zn 1/2 Ta 2/3 )O 3 And (1-z) SrTiO 3 -zBiFeO 3 Bi may be 0.39 Na 0.36 Sr 0.25 TiO 3 And BaBi 2 Nb 2 O 9 May also be (1-x-y) BiFeO 3 -xBaTiO 3 -yBa(Zn 1/2 Ta 2/3 )O 3 And BaBi 2 Nb 2 O 9 Bi may be used 0.39 Na 0.36 Sr 0.25 TiO 3 And (1-z) SrTiO 3 -zBiFeO 3 . The minimum thickness of the laminated structure can reach 25 mu m, the maximum thickness is not limited, and different laminated thicknesses can be selected according to actual use requirements.
In addition, the layered structure of the ceramic dielectric according to the present invention is not limited to a single layered structure formed by one first dielectric layer and one second dielectric layer, and may be any layered combination of the first dielectric layer and the second dielectric layer, for example, a layered structure formed by layering two first dielectric layers and one second dielectric layer, a layered structure formed by layering one first dielectric layer and two second dielectric layers, a layered structure formed by layering two first dielectric layers and three second dielectric layers, and the like. As shown in fig. 2 and 3. Different arrangement modes can be selected according to actual use requirements.
The layered ceramic medium with high energy storage density and high energy storage efficiency is formed by alternately laminating high-polarization-intensity medium layers, high-compressive strength and high-energy storage-efficiency medium layers of different materials, can integrate excellent performances of the two different materials, not only improves the energy storage density of lead-free ceramics, but also can promote the energy storage efficiency to be greatly improved, and further obtains excellent comprehensive performance. In addition, the thickness of the ceramic medium can reach 25 mu m at least, which is far lower than that of the traditional granulating and pressing ceramic medium, and the electric property test and the energy storage property calculation can be directly carried out, so that polishing is not needed, and the preparation cost and the preparation period are saved.
The second aspect of the invention provides a method for preparing a layered ceramic medium with high energy storage density and high energy storage efficiency, comprising the following steps:
s1, respectively weighing corresponding oxides or carbonates according to chemical formulas of the first material and the second material to obtain the first material and the second material, wherein the first material has high polarization strength, and the second material has high compressive strength and high energy storage efficiency.
The first material in this step comprises (1-x-y) BiFeO 3 -xBaTiO 3 -yBa(Zn 1/2 Ta 2/3 )O 3 And Bi (Bi) 0.39 Na 0.36 Sr 0.25 TiO 3 Wherein x=0.30-0.40 and y=0.05-0.15, the second material comprises (1-z) SrTiO 3 -zBiFeO 3 And BaBi 2 Nb 2 O 9 Wherein z=0.25-0.35.
Weighing corresponding oxide or carbonate according to chemical formulas of the first material and the second material respectively, namely (1-x-y) BiFeO is selected as the first material 3 -xBaTiO 3 -yBa(Zn 1/2 Ta 2/3 )O 3 ThenCorrespondingly weighing Bi 2 O 3 、Fe 2 O 3 、BaCO 3 、TiO 2 ZnO and Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the First material selection Bi 0.39 Na 0.36 Sr 0.25 TiO 3 Correspondingly weighing Bi 2 O 3 、Na 2 CO 3 、SrCO 3 And TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Second material selection (1-z) SrTiO 3 -zBiFeO 3 Correspondingly weigh SrCO 3 、TiO 2 、Bi 2 O 3 And Fe (Fe) 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The second material is BaBi 2 Nb 2 O 9 Correspondingly weigh BaCO 3 、Bi 2 O 3 And Nb (Nb) 2 O 5 。
It should be noted that the oxide or carbonate corresponding to the first material and the second material is preferably of an analytically pure grade.
S2, respectively performing first ball milling on the first raw material and the second raw material for 4-24 hours; and drying at 80-100deg.C.
And respectively performing first ball milling on the first raw material and the second raw material to ensure that all substances in the first raw material are uniformly mixed, and all substances in the second raw material are uniformly mixed. The ball milling medium adopted in the first ball milling is zirconia balls and absolute ethyl alcohol.
And S3, calcining the raw materials subjected to ball milling and drying for the first time at 800-900 ℃ for 2-4 hours respectively to obtain a pre-synthesized phase composition.
Specifically, the calcination in this step may be performed in a crucible made of alumina, zirconia, or the like.
S4, respectively performing secondary ball milling on the pre-synthesized phase composition, wherein the ball milling time is 4-24 hours.
The purpose of the second ball milling is to make the particles of the pre-synthesized raw material powder as fine as possible, so that high-quality casting forming slurry and ceramic film can be obtained in the later stage.
Meanwhile, as a preferential scheme, in the second ball milling, mnO with the weight ratio of 0.1 to 0.2 percent can be added according to the mass ratio of the raw material powder 2 Or 0.1 to 0.2wt% MnCO 3 Or 0.1 to 0.2wt% Mn 3 O 4 Etc. to prevent the price change of iron at high temperature, change the performance, and adjust the sintering temperature so that the sintering temperature of the two materials is close and the sintering matching property is improved. Added MnO 2 Or MnCO 3 Or Mn of 3 O 4 Preferably, the purity is more than or equal to 99 percent.
S5, drying and sieving the raw materials subjected to the second ball milling at 80-100 ℃ respectively to obtain ceramic powder.
Specifically, the sieving in this step may be selected to be 120 mesh sieving.
S6, mixing the first organic solution for 4-6 hours, adding the second organic solution, the binder and the ceramic powder into the first organic solution, and mixing for 4-6 hours again to obtain the first ceramic slurry and the second ceramic slurry for tape casting.
Wherein the first organic solution is a mixed solution of absolute ethyl alcohol, butanone and triolein, and the mass ratio of the absolute ethyl alcohol, the butanone and the triolein is as follows: 40-60:80-120:3-6. In the proportion range, the phenomenon of peeling of the surface of the slurry caused by the drying speed of the casting film can be effectively reduced, the agglomeration phenomenon of powder particles can be inhibited, and the dispersibility and uniformity of the slurry are improved.
The second type of organic solution is a mixed solution of dibutyl phthalate and polyethylene glycol, and the mass ratio of the dibutyl phthalate to the polyethylene glycol is 1:1. Within this ratio range, the obtained cast film has excellent flexibility, workability, and plasticity.
The binder used in this step is preferably polyvinyl butyral.
In addition, in order to achieve better dissolution effect and further improve film forming quality, the addition amount of butanone in the first organic solution in the step is 80% -100% of the mass of ceramic powder, the addition amount of dibutyl phthalate and polyethylene glycol in the second organic solution is 2% -5% of the mass of ceramic powder, and the addition amount of the binder is 8% -15% of the mass of ceramic powder.
It should be noted that the first type of organic solution may be mixed by ball milling and magnetic stirring, preferably by ball milling, and the ball milling medium includes zirconia balls, wherein the adding amount of the zirconia balls is 1.5-2.5 times of the mass of the ceramic powder.
The casting dope obtained in the above proportions in this step has very good fluidity, and a thin layer casting film of high quality can be obtained without performing a vacuum bubble removal (bubble removal of the dope) process.
S7, preparing the first ceramic slurry and the second ceramic slurry into a high-polarization-strength film, a high-compressive strength film and a high-energy-storage-efficiency film through tape casting and forming processes respectively; wherein the height of the doctor blade in the casting molding process is 80-200 mu m.
And placing the prepared high-polarization-strength film, high-compressive strength and high-energy-storage-efficiency film in a clean and dry environment at room temperature to fully volatilize volatile organic matters.
S8, cutting, laminating, pressing and other processes are carried out on the high-polarization-strength film, the high-compressive-strength film and the high-energy-storage-efficiency film to obtain ceramic green bodies with different layered structures.
The pressing process in this step is preferably:
pressurizing at 30-60deg.C with pressures of 50MPa, 100MPa, 150MPa, 200MPa, and 250MPa for 8-10 min. The pressing method can eliminate air holes among the films as much as possible, and improves the quality of the films.
S9, performing glue discharging treatment on the ceramic green body at 550-600 ℃, wherein the heat preservation time is 8-10h, and then sintering the ceramic green body subjected to glue discharging under a closed condition, so as to finally obtain the layered ceramic medium with high energy storage density and high energy storage efficiency.
In order to further improve the quality of the ceramic medium, the sintering process in this step is preferably:
raising the temperature from room temperature to 1060-1200 ℃ at a heating rate of 3-5 ℃/min, then lowering the temperature to 960-1080 ℃ at a cooling rate of 15-20 ℃/min, preserving the temperature for 2-4h, and then naturally cooling to the room temperature along with the furnace.
The layered high energy storage density and high energy storage efficiency ceramic medium and the method for preparing the same according to the present invention are described in detail below with reference to specific examples.
Example 1
The layered ceramic medium with high energy storage density and high energy storage efficiency of the embodiment has the material of the high polarization intensity medium layer of 0.60BiFeO 3 -0.34BaTiO 3 -0.06Ba(Zn 1/2 Ta 2/3 )O 3 The method comprises the steps of carrying out a first treatment on the surface of the The material of the dielectric layer with high compressive strength and high energy storage efficiency is BaBi 2 Nb 2 O 9 . A schematic cross-sectional view of a layered ceramic dielectric is shown in fig. 1.
The preparation method of the layered ceramic medium with high energy storage density and high energy storage efficiency comprises the following steps:
(1) Selecting Bi with purity more than 98 percent 2 O 3 、Fe 2 O 3 、BaCO 3 、TiO 2 、ZnO、Nb 2 O 5 And Ta 2 O 5 As the raw material of layered ceramic medium with high energy storage density and high energy storage efficiency, and respectively according to chemical formula 0.60BiFeO 3 -0.34BaTiO 3 -0.06Ba(Zn 1/2 Ta 2/3 )O 3 And BaBi 2 Nb 2 O 9 Weighing the corresponding raw materials respectively to obtain 80 g in total;
(2) The weighed raw materials are uniformly mixed through a ball milling process (first ball milling), and are dried at 80 ℃ to obtain initial raw material powder, wherein the adopted ball milling media are zirconium oxide balls and absolute ethyl alcohol, the adding amount of the zirconium oxide balls and the absolute ethyl alcohol is 150 g and 100 ml respectively, and the ball milling time is 4h;
(3) Calcining the raw material powder in a zirconia crucible for 2 hours to obtain a pre-synthesized phase composition, wherein 0.60BiFeO 3 -0.34BaTiO 3 -0.06Ba(Zn 1/2 Ta 2/3 )O 3 And BaBi 2 Nb 2 O 9 The calcination temperature of the catalyst is 800 ℃, and the temperature rising rate is 5 ℃/min;
(4) Weighing 50 g of the calcined raw material, and adding the calcined raw material into 0.60BiFeO 3 -0.34BaTiO 3 -0.06Ba(Zn 1/2 Ta 2/3 )O 3 To which 0.2wt% MnO was added 2 (purity is more than or equal to 99 percent), and the mixture is placed in a ball milling tank again for secondary ball milling, so that the particles of the pre-synthesized raw material powder are as fine as possibleThe high-quality casting forming slurry and ceramic membrane are convenient to obtain in the later stage, wherein the ball milling medium adopted is zirconia balls and absolute ethyl alcohol, the adding amount of the zirconia balls and the absolute ethyl alcohol is 100 g and 60 ml respectively, and the ball milling time is 24 hours;
(5) Drying the raw materials subjected to the second ball milling at 80 ℃ and sieving the raw materials with a 120-mesh sieve to obtain 0.60BiFeO 3 -0.34BaTiO 3 -0.06Ba(Zn 1/2 Ta 2/3 )O 3 And BaBi 2 Nb 2 O 9 Ceramic powder;
(6) 40 g of zirconia balls, 9 g of absolute ethyl alcohol, 20 g of butanone and 0.8 g of triolein are weighed and placed in a ball milling tank with a volume of 150 ml to be ball milled for 4 hours at a speed of 300 revolutions per minute, and then 0.7 g of dibutyl phthalate, 0.7 g of polyethylene glycol, 1.8 g of polyvinyl butyral and 20 g of 0.60BiFeO are weighed and added 3 -0.34BaTiO 3 -0.06Ba(Zn 1/ 2 Ta 2/3 )O 3 Or 20 g of BaBi 2 Nb 2 O 9 Ball milling the ceramic powder for 4 hours at the rotating speed of 300 revolutions per minute again to obtain ceramic slurry for tape casting;
(7) The ceramic slurry obtained above is respectively prepared into 0.60BiFeO with high polarization intensity through tape casting and forming process 3 -0.34BaTiO 3 -0.06Ba(Zn 1/2 Ta 2/3 )O 3 Ceramic membrane and BaBi with high compressive strength and high energy storage efficiency 2 Nb 2 O 9 Placing the ceramic film in a clean and dry environment for 2 days at room temperature, wherein the height of a scraper in the casting forming process is 80 mu m;
(8) Cutting, laminating, pressing and other processes are carried out on the obtained ceramic film to obtain ceramic green bodies with different laminated structures, wherein the pressing process is to sequentially adopt pressures of 50MPa, 100MPa, 150MPa, 200MPa and 250MPa at 40 ℃, the dwell time under each pressure is 8 minutes, and the laminating process is shown in figure 4;
(9) And (3) performing glue discharging treatment on the obtained ceramic blank at 550 ℃, wherein the heat preservation time is 10 hours, then sintering the ceramic blank after glue discharging under a closed condition to obtain the layered structure lead-free ceramic sample with high energy storage density and high energy storage efficiency, wherein the sintering process is that the temperature is raised to 1060 ℃ from room temperature at a heating rate of 5 ℃/min, then the temperature is lowered to 960 ℃ at a cooling rate of 15 ℃/min, and the heat preservation is performed for 2 hours, and then the layered ceramic medium with high energy storage density and high energy storage efficiency of the embodiment is obtained after natural cooling to the room temperature along with a furnace.
The ferroelectric analyzer was used to test the hysteresis loops of the layered high energy storage density and high energy storage efficiency ceramic media prepared in this example under different electric field intensities, as shown in fig. 5. The effective energy storage density of the layered structure ceramic of the embodiment under the electric field strength of 230kV/cm calculated based on the formulas (1) and (2) is 0.6J/cm 3 The energy storage efficiency is 86%.
Example two
The layered ceramic medium with high energy storage density and high energy storage efficiency of the embodiment has the material of Bi as the medium layer with high polarization intensity 0.39 Na 0.36 Sr 0.25 TiO 3 The method comprises the steps of carrying out a first treatment on the surface of the The material of the dielectric layer with high compressive strength and high energy storage efficiency is 0.65SrTiO 3 -0.35BiFeO 3 。
The preparation method of the layered ceramic medium with high energy storage density and high energy storage efficiency comprises the following steps:
(1) Selecting Bi with purity more than 98 percent 2 O 3 、Fe 2 O 3 、SrCO 3 、Na 2 CO 3 And TiO 2 As the raw materials of the layered ceramic medium with high energy storage density and high energy storage efficiency in the embodiment, the material is respectively prepared according to the chemical formula Bi 0.39 Na 0.36 Sr 0.25 TiO 3 And 0.65SrTiO 3 -0.35BiFeO 3 Weighing the corresponding raw materials to total 80 g;
(2) The weighed raw materials are uniformly mixed through a ball milling process (first ball milling), and are dried at 100 ℃ to obtain initial raw material powder, wherein the adopted ball milling media are zirconium oxide balls and absolute ethyl alcohol, the adding amount of the zirconium oxide balls and the absolute ethyl alcohol is 150 g and 100 ml respectively, and the ball milling time is 24h;
(3) Calcining the raw material powder in a crucible made of aluminaFiring for 4h to obtain a pre-synthesized phase composition, wherein Bi 0.39 Na 0.36 Sr 0.25 TiO 3 And 0.65SrTiO 3 -0.35BiFeO 3 The calcination temperature of (2) is 850 ℃ and 900 ℃ respectively, and the temperature rising rate is 3 ℃/min;
(4) Weighing 50 g of the calcined raw material, and adding 0.65SrTiO 3 -0.35BiFeO 3 Adding 0.1wt% of MnCO 3 (purity is more than or equal to 99%), ball milling is carried out again in a ball milling tank for the second time, so that the particles of the pre-synthesized raw material powder are as fine as possible, and high-quality tape casting slurry and ceramic membrane can be conveniently obtained in the later stage, wherein the ball milling medium is zirconia balls and absolute ethyl alcohol, the adding amount of the zirconia balls and the absolute ethyl alcohol is respectively 100 g and 60 ml, and the ball milling time is 24 hours;
(5) Drying the raw materials subjected to the second ball milling at 100 ℃ and sieving the raw materials with a 120-mesh sieve to obtain Bi 0.39 Na 0.36 Sr 0.25 TiO 3 And 0.65SrTiO 3 -0.35BiFeO 3 Ceramic powder;
(6) 40 g of zirconia balls, 9 g of absolute ethyl alcohol, 20 g of butanone, 0.8 g of triolein are weighed and placed in a ball milling tank with a volume of 150 ml to be ball milled for 6 hours at a speed of 500 revolutions per minute, and then 0.8 g of dibutyl phthalate, 0.8 g of polyethylene glycol, 1.8 g of polyvinyl butyral and 20 g of Bi are weighed and added 0.39 Na 0.36 Sr 0.25 TiO 3 Or 20 g of 0.65SrTiO 3 -0.35BiFeO 3 Ball milling the ceramic powder for 6 hours at the rotating speed of 500 revolutions per minute again to obtain ceramic slurry for tape casting;
(7) Respectively preparing Bi with high polarization strength from the ceramic slurry through a tape casting process 039 Na 036 Sr 025 TiO 3 Ceramic film and 0.65SrTiO with high compressive strength and high energy storage efficiency 3 -0.35BiFeO 3 The ceramic film is placed in a clean and dry environment at room temperature for 2 days, wherein the higher the height of the scraper is, the thicker the thickness of the ceramic film obtained by casting molding is. In order to obtain thinner ceramic films and ceramic media under the condition of guaranteeing uniformity, the doctor blade in the casting molding process of the embodimentThe height is 120 μm, and the thickness of the dried ceramic film is about 10 μm;
(8) Cutting, laminating, pressing and other processes are carried out on the obtained ceramic film to obtain a layered structure ceramic green body shown in fig. 6, wherein the pressing process is to sequentially adopt pressures of 50MPa, 100MPa, 150MPa, 200MPa and 250MPa at 45 ℃ for pressurizing, and the pressure maintaining time under each pressure is 10 minutes;
(9) And (3) performing glue discharging treatment on the obtained ceramic blank at 600 ℃, wherein the heat preservation time is 8 hours, then sintering the ceramic blank after glue discharging in a buried firing mode under a closed condition, and finally obtaining the layered structure lead-free ceramic sample with high energy storage density and high energy storage efficiency, wherein the sintering process is that the temperature is increased from room temperature to 1220 ℃ at a heating rate of 3 ℃/min, then the temperature is reduced to 1080 ℃ at a cooling rate of 20 ℃/min, and the temperature is kept for 3 hours, and then the ceramic blank is naturally cooled to the room temperature along with a furnace.
Because the thickness of the ceramic film obtained by casting in the embodiment is thinner, the total thickness of the layered ceramic medium prepared by lamination, sintering and other processes is only 25 mu m, and the electrical performance test can be performed by plating the electrode without thinning. The ferroelectric analyzer was used to test the ferroelectric hysteresis loop of the prepared layered ceramic as shown in fig. 7. The effective energy storage density of the layered structure ceramic of the embodiment under the electric field intensity of 710kV/cm calculated based on the formulas (1) and (2) is 9.05J/cm 3 The corresponding energy storage efficiency can reach more than 95%, and meanwhile, higher energy storage density and energy storage efficiency are realized.
The layered ceramic medium with high energy storage density and high energy storage efficiency and the preparation method thereof are characterized in that the ceramic medium is formed by alternately laminating the dielectric layers with high polarization intensity, high compressive strength and high energy storage efficiency, and can integrate excellent performances of two different materials, thereby not only improving the energy storage density of lead-free ceramics, but also promoting the energy storage efficiency to be greatly improved, and further obtaining excellent comprehensive performances. Meanwhile, the preparation method can effectively improve the sintering matching performance of layered heterogeneous ceramics, and can overcome the problem that the energy storage density and the energy storage efficiency of the existing lead-free energy storage ceramic medium are difficult to synergistically enhance, so that the ceramic medium with high energy storage density and high energy storage efficiency is obtained.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (10)
1. A layered ceramic medium with high energy storage density and high energy storage efficiency is characterized in that the layered ceramic medium with high energy storage density and high energy storage efficiency is of a layered structure formed by alternately stacking a first dielectric layer and a second dielectric layer, wherein the first dielectric layer is a dielectric layer with high polarization intensity, and the material of the dielectric layer with high polarization intensity comprises (1-x-y) BiFeO 3 -xBaTiO 3 -yBa(Zn 1/2 Ta 2/3 )O 3 And Bi (Bi) 0.39 Na 0.36 Sr 0.25 TiO 3 Wherein x=0.30-0.40 and y=0.05-0.15; the second dielectric layer is a dielectric layer with high compressive strength and high energy storage efficiency, and the material of the dielectric layer with high compressive strength and high energy storage efficiency comprises (1-z) SrTiO 3 -zBiFeO 3 And BaBi 2 Nb 2 O 9 Wherein z=0.25-0.35; the thickness of the layered structure is at least 25 μm.
2. The preparation method of the layered ceramic medium with high energy storage density and high energy storage efficiency is characterized by comprising the following steps:
respectively weighing corresponding oxides or carbonates according to chemical formulas of the first material and the second material to obtain a first raw material and a second raw material, wherein the first material has high polarization strength, and the second material has high compressive strength and high energy storage efficiency;
respectively performing first ball milling on the first raw material and the second raw material for 4-24 hours; drying at 80-100deg.C;
calcining the raw materials subjected to ball milling and drying for 2-4 hours at 800-900 ℃ respectively to obtain a pre-synthesized phase composition;
respectively performing secondary ball milling on the pre-synthesized phase composition for 4-24 hours;
drying and sieving the raw materials subjected to the second ball milling at 80-100 ℃ respectively to obtain ceramic powder;
firstly mixing a first organic solution for 4-6 hours, then adding a second organic solution, a binder and the ceramic powder into the first organic solution, and mixing again for 4-6 hours to obtain a first ceramic slurry and a second ceramic slurry for tape casting;
preparing the first ceramic slurry and the second ceramic slurry into a high-polarization-strength film, a high-compressive strength film and a high-energy-storage-efficiency film through tape casting and forming processes respectively; wherein the height of the scraper in the casting forming process is 80-200 mu m;
cutting, laminating, pressing and other processes are carried out on the high-polarization-strength film, the high-compressive-strength film and the high-energy-storage-efficiency film to obtain ceramic green bodies with different layered structures;
and (3) carrying out glue discharging treatment on the ceramic green body at 550-600 ℃, wherein the heat preservation time is 8-10h, and then sintering the ceramic green body subjected to glue discharging under a closed condition, so as to finally obtain the layered ceramic medium with high energy storage density and high energy storage efficiency.
3. The method of claim 2, wherein the first feedstock comprises (1-x-y) BiFeO 3 -xBaTiO 3 -yBa(Zn 1/2 Ta 2/3 )O 3 And Bi (Bi) 0.39 Na 0.36 Sr 0.25 TiO 3 Wherein x=0.30-0.40 and y=0.05-0.15, and the second raw material comprises (1-z) SrTiO 3 -zBiFeO 3 And BaBi 2 Nb 2 O 9 Wherein z=0.25-0.35.
4. The method according to claim 3, wherein the (1-x-y) BiFeO 3 -xBaTiO 3 -yBa(Zn 1/2 Ta 2/3 )O 3 Corresponding oxides orThe carbonate comprises Bi 2 O 3 、Fe 2 O 3 、BaCO 3 、TiO 2 ZnO and Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the The Bi is 0.39 Na 0.36 Sr 0.25 TiO 3 The corresponding oxide or carbonate comprises Bi 2 O 3 、Na 2 CO 3 、SrCO 3 And TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The (1-z) SrTiO 3 -zBiFeO 3 The corresponding oxide or carbonate comprises SrCO 3 、TiO 2 、Bi 2 O 3 And Fe (Fe) 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The BaBi 2 Nb 2 O 9 The corresponding oxide or carbonate comprises BaCO 3 、Bi 2 O 3 And Nb (Nb) 2 O 5 。
5. The preparation method according to claim 2, wherein the first organic solution is a mixed solution of absolute ethyl alcohol, butanone and triolein, and the mass ratio of the absolute ethyl alcohol, the butanone and the triolein is: 40-60:80-120:3-6.
6. The preparation method according to claim 5, wherein the addition amount of butanone in the first type of organic solution is 80% -100% of the mass of the ceramic powder.
7. The preparation method according to claim 2, wherein the second type of organic solution is a mixed solution of dibutyl phthalate and polyethylene glycol, and the mass ratio of dibutyl phthalate to polyethylene glycol is 1:1.
8. The preparation method of claim 7, wherein the addition amount of dibutyl phthalate and polyethylene glycol in the second type of organic solution is 2% -5% of the mass of the ceramic powder.
9. The preparation method according to claim 2, wherein the addition amount of the binder is 8% -15% of the mass of the ceramic powder.
10. The method according to claim 2, wherein the first type of organic solution is mixed by a ball milling process, and the ball milling medium comprises zirconia balls, wherein the adding amount of the zirconia balls is 1.5-2.5 times of the mass of the ceramic powder.
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