CN109734440B - SrTiO with heterogeneous layered structure3Base energy storage medium ceramic and preparation method thereof - Google Patents
SrTiO with heterogeneous layered structure3Base energy storage medium ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses SrTiO with a heterogeneous layered structure3Base energy storage dielectric ceramic, preparation method thereof and SrTiO with heterogeneous layered structure3The preparation method of the base energy storage medium ceramic comprises the step of modifying SrTiO3Ceramic green ceramic band and TiO based energy storage medium2Raw porcelain band and modified SrTiO3Sequentially stacking and placing the base energy storage medium ceramic green ceramic tapes to form a sandwich structure, carrying out cold isostatic pressing to obtain a composite biscuit, carrying out binder removal on the composite biscuit, and sintering at the temperature of 1220-3A base energy storage ceramic. The invention is in SrTiO3Rutile TiO with relatively low dielectric constant and high insulation is introduced into base ceramic2The ceramic layer forms heterogeneous layered dielectric ceramic with a sandwich structure, and greatly improves SrTiO3The breakdown field intensity of the base energy storage dielectric ceramic ensures that the dielectric ceramic can work under higher voltage. SrTiO with heterogeneous layered structure prepared by the invention3The maximum energy storage density of the base energy storage medium ceramic is from 1.7J/cm3Increased to 9.4J/cm3。
Description
Technical Field
The invention relates to the field of energy storage medium ceramics, in particular to SrTiO with a heterogeneous layered structure3A base energy storage medium ceramic and a preparation method thereof.
Background
The energy storage dielectric ceramic has the characteristics of heavy current discharge and rapid charge and discharge, and is widely applied to the fields of military industry, medical treatment, environmental treatment and the like. The density of stored energy is in direct proportion to the dielectric constant of the dielectric ceramic and the quadratic power of breakdown field intensity. Therefore, to obtain a dielectric ceramic material with high energy storage density, it is necessary to increase its dielectric constant and increase its breakdown field strength. SrTiO3 has high dielectric constant (290 @1KHz), low dielectric loss (0.01 @1KHz) and high theoretical breakdown field strength (1600kV/cm), and is a representative material of energy storage dielectric ceramics. However, the actual breakdown field strength (8-12kV/mm) is much smaller than its theory due to unavoidable microstructural defects caused during the ceramic preparation process. In order to increase the energy storage density, especially the breakdown field strength, the traditional method is to adopt the means of ion replacement, adding low-melting-point sintering aid and the like to make the ceramic have a uniform and fine-grained microstructure.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides modified SrTiO3Base energy storage dielectric ceramic, preparation method thereof and SrTiO with heterogeneous layered structure3A base energy storage medium ceramic and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme: modified SrTiO3The base energy storage dielectric ceramic comprises 100 parts of SrTiO by mass35-8 parts of Pb3O42-4 parts of Bi2O30.5-1 part of SiO20.8-1.5 parts of Al2O3。
Modified SrTiO3The preparation method of the base energy storage medium ceramic comprises the following steps of mixing 100 parts by mass of SrTiO35-8 parts of Pb3O42-4 parts of Bi2O30.5-1 part of SiO20.8-1.5 parts of Al2O3Grinding and mixing uniformly, wherein 100 parts of SrTiO3The SrTiO3Formed by SrCO with the molar ratio of 1:13And TiO2Prepared at high temperature; after being mixed evenly, the mixture is calcined for 3 hours at 900 ℃, and SrTiO can be obtained3And (3) base energy storage medium ceramic.
Preferably, the TiO is2The rutile type is selected.
SrTiO with heterogeneous layered structure3Based energy storage dielectric ceramic comprising TiO prepared by tape casting technique2Green ceramic tape and modified SrTiO3A ceramic green ceramic tape based on an energy storage medium, said TiO2Two modified SrTiO raw porcelain tapes3An interlayer of a base energy storage medium ceramic green ceramic tape.
Preferably, the modified SrTiO3The base energy storage medium is a raw ceramic tape of 28-32 microns and TiO2The thickness of the green tape is 3-15 microns.
Preferably, two of the modified SrTiO3The thickness of the base energy storage medium green ceramic tape is the same, and TiO2The thickness of the raw porcelain band accounts for two modified SrTiO310-20% of the total thickness of the base energy storage medium green ceramic tape.
Preferably, the SrTiO with the heterogeneous layered structure3The dielectric constant of the base energy storage medium ceramic is 2700 +/-200 at 1KHz and the loss<0.01, resistivity>5×1011Omega cm, breakdown field strength>20kV/mm。
Preferably, the SrTiO with the heterogeneous layered structure3The maximum energy storage density of the base energy storage medium ceramic is 1.7J/cm3Increased to 9.4J/cm3。
SrTiO with heterogeneous layered structure3Preparation method of base energy storage medium ceramic, SrTiO with heterogeneous layered structure3Ceramic package based on energy storage mediumComprises TiO2Green ceramic tape and modified SrTiO described above3Based energy storage medium ceramic green ceramic tape, the modified SrTiO3Ceramic green ceramic band and TiO based energy storage medium2Raw porcelain band and modified SrTiO3Sequentially stacking and placing the base energy storage medium ceramic green ceramic tapes to form a sandwich structure, carrying out cold isostatic pressing to obtain a composite biscuit, carrying out binder removal on the composite biscuit, and sintering at the temperature of 1220-3A base energy storage ceramic.
Preferably, the pressure in the cold isostatic pressing process is 120-180MPa, and the pressure maintaining time is 90-180 seconds.
The invention has the beneficial effects that:
1. the invention is in SrTiO3Rutile TiO with relatively low dielectric constant and high insulation is introduced into base ceramic2The ceramic layer forms heterogeneous layered dielectric ceramic with a sandwich structure, and greatly improves SrTiO3The breakdown field intensity of the base energy storage dielectric ceramic ensures that the dielectric ceramic can work under higher voltage.
2. SrTiO with heterogeneous layered structure prepared by the invention3The maximum energy storage density of the base energy storage medium ceramic is from 1.7J/cm3Increased to 9.4J/cm3。
Drawings
FIG. 1 shows a heterogeneous layered SrTiO3A ceramic microscopic structure diagram of a base energy storage medium;
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
Preparation of modified SrTiO by tape casting technology3Ceramic green ceramic tape (A) and TiO based energy storage medium2A raw porcelain band (B) which is formed by a ceramic band,
modified SrTiO3The preparation method of the ceramic green tape (A) based on the energy storage medium comprises the steps of firstly obtaining the modified SrTiO3Grinding the base energy storage medium ceramic to obtain modified SrTiO with the average particle size of 0.7-1um3Based on energy-storing dielectric ceramic powder, modified SrTiO3Base storeThe energy medium ceramic powder is pretreated at the temperature of 130-140 ℃, and then the pretreated SrTiO is treated3Adding the base energy storage medium ceramic powder into a casting medium, ball-milling and uniformly mixing for 8-12h in a closed environment, defoaming in vacuum, adopting a scraper method for casting molding, adding a binder a on the surface, and drying to obtain the modified SrTiO3The energy-storage medium ceramic green ceramic tape (A) is prepared by mixing a casting medium with a solvent, a binder b, a plasticizer and a dispersant, wherein the solvent is ethanol, the binder a is polyvinyl alcohol, and the addition amount of the polyvinyl alcohol is such that modified SrTiO can be obtained3Ceramic green ceramic band (A) and TiO based energy storage medium2The raw porcelain tapes (B) are bonded together, the binder B is a mixture of ethyl methacrylate and methacrylic acid, and the plasticizer and the dispersant respectively adopt dibutyl phthalate and ammonium polyacrylate in parts by mass, and the modified SrTiO is3The ceramic green porcelain tape (A) of the base energy storage medium comprises 100 parts of modified SrTiO3The energy storage medium comprises base energy storage medium ceramic powder, 10-12 parts of ethanol, 7-8 parts of binder b, 2-3 parts of dibutyl phthalate and 3-15 parts of ammonium polyacrylate, wherein the weight percentage of ethyl methacrylate and methacrylic acid in the binder b is 2: 1.
TiO2The preparation method of the green tape (B) comprises the steps of firstly selecting TiO with the average grain diameter of 0.7-1um2Powder of TiO2Pretreating the powder at the temperature of 130 ℃ and 140 ℃, and then carrying out pretreatment on the TiO2Adding the powder into a casting medium, ball-milling and uniformly mixing for 8-12h in a closed environment, defoaming in vacuum, carrying out casting molding by adopting a scraper method, adding a binder a on the surface, and drying to obtain TiO2The green ceramic band (B) is prepared from the mixture of solvent, adhesive (B), plasticizer and disperser, the solvent is alcohol, the adhesive (a) is polyvinyl alcohol, and the polyvinyl alcohol is added in such an amount that the modified SrTiO can be obtained3Ceramic green ceramic band (A) and TiO based energy storage medium2Raw porcelain band (B), modified SrTiO3The energy-storage medium ceramic green ceramic tape (A) can be adhered together when being laminated, the binder b is a mixture of ethyl methacrylate and methacrylic acid, and the plasticizer and the dispersant respectively adopt dibutyl phthalate and ammonium polyacrylate in parts by mass, namely TiO2Raw porcelain band(B) Comprises 100 parts of modified SrTiO3The energy storage medium comprises base energy storage medium ceramic powder, 10-12 parts of ethanol, 9-10 parts of binder b, 5-6 parts of dibutyl phthalate and 3-15 parts of ammonium polyacrylate, wherein the weight percentage of ethyl methacrylate and methacrylic acid in the binder b is 2: 1.
Modified SrTiO3The film thickness of the base energy storage medium ceramic green ceramic tape (A) is 28-32 microns, and TiO2The green tape (B) has a film thickness of 3-15 μm and is made of TiO2The thickness of the green ceramic tape (B) accounts for two modified SrTiO310-20% of the total thickness of the base energy storage medium green porcelain tape (A).
Example 1
Modified SrTiO3The preparation method of the base energy storage medium ceramic comprises the following steps of:
s1, mixing SrCO with the molar ratio of 1:13And TiO2SrTiO made at high temperature3，
S2, mixing 100 parts of SrTiO35 parts of Pb3O42 parts of Bi2O30.5 part of SiO20.8 part of Al2O3Grinding and mixing uniformly;
s3, calcining for 3 hours at 900 ℃ after uniform mixing to obtain modified SrTiO3And (3) base energy storage medium ceramic.
SrTiO with heterogeneous layered structure3The preparation method of the base energy storage medium ceramic comprises the following steps:
s4, modifying SrTiO3Ceramic green ceramic band (A) and TiO based energy storage medium2Raw porcelain band (B), modified SrTiO3The ceramic green porcelain tapes (A) of the base energy storage medium are stacked according to A-B-A to form a sandwich structure; wherein, the modified SrTiO is prepared by adopting a tape casting technology3Ceramic green ceramic tape (A) and TiO based energy storage medium2A raw porcelain band (B) which is formed by a ceramic band,
specifically, modified SrTiO3The preparation method of the ceramic green porcelain tape (A) based on the energy storage medium comprises the steps of firstly, obtaining modified SrTiO3 from S33Grinding the base energy storage medium ceramic to obtain modified SrTiO with the average particle size of 0.7um3Based on energy-storing dielectric ceramic powder, modified SrTiO3Pretreating base energy storage dielectric ceramic powder at 130 ℃, and then pretreating SrTiO3Adding the base energy storage medium ceramic powder into a casting medium, ball-milling and uniformly mixing for 8h in a closed environment, defoaming in vacuum, adopting a scraper method for casting, adding a binder a on the surface, and drying to obtain the modified SrTiO3The energy-storage medium ceramic green ceramic tape (A) is prepared by mixing a casting medium with a solvent, a binder b, a plasticizer and a dispersant, wherein the solvent is ethanol, the binder a is polyvinyl alcohol, and the addition amount of the polyvinyl alcohol is such that modified SrTiO can be obtained3Ceramic green ceramic band (A) and TiO based energy storage medium2The raw porcelain tapes (B) are bonded together, the binder B is a mixture of ethyl methacrylate and methacrylic acid, and the plasticizer and the dispersant respectively adopt dibutyl phthalate and ammonium polyacrylate in parts by mass, and the modified SrTiO is3The ceramic green porcelain tape (A) of the base energy storage medium comprises 100 parts of modified SrTiO3The energy storage medium comprises base energy storage medium ceramic powder, 10 parts of ethanol, 7 parts of binder b, 2 parts of dibutyl phthalate and 3 parts of ammonium polyacrylate, wherein the weight percentage of ethyl methacrylate and methacrylic acid in the binder b is 2: 1.
TiO2A process for producing a green tape (B) comprises selecting TiO with an average particle diameter of 0.7um2Powder of TiO2Pretreating the powder at 130 deg.C, and then adding pretreated TiO2Adding the powder into a casting medium, ball-milling and uniformly mixing for 8-12h in a closed environment, defoaming in vacuum, carrying out casting molding by adopting a scraper method, adding a binder a on the surface, and drying to obtain TiO2The green ceramic band (B) is prepared from the mixture of solvent, adhesive (B), plasticizer and disperser, the solvent is alcohol, the adhesive (a) is polyvinyl alcohol, and the polyvinyl alcohol is added in such an amount that the modified SrTiO can be obtained3Ceramic green ceramic band (A) and TiO based energy storage medium2Raw porcelain band (B), modified SrTiO3The energy-storage medium ceramic green ceramic tape (A) can be adhered together when being laminated, the binder b is a mixture of ethyl methacrylate and methacrylic acid, and the plasticizer and the dispersant respectively adopt dibutyl phthalate and ammonium polyacrylate in parts by mass, namely TiO2The green tape (B) comprises 100 part of modified SrTiO3The energy storage medium comprises base energy storage medium ceramic powder, 10 parts of ethanol, 9 parts of binder b, 5 parts of dibutyl phthalate and 3 parts of ammonium polyacrylate, wherein the weight percentage of ethyl methacrylate and methacrylic acid in the binder b is 2: 1.
Modified SrTiO3The film thickness of the base energy storage medium ceramic green ceramic tape (A) is 28 microns, and TiO2The thickness of the green tape (B) was 5 μm
S5, carrying out cold isostatic pressing on the A-B-A structure to obtain an A-B-A composite biscuit, wherein the pressure intensity is 120MPa in the cold isostatic pressing process, and the pressure maintaining time is 90 seconds;
s6, removing the glue from the composite biscuit, and sintering at 1220 ℃ for 1 hour to obtain the SrTiO with the heterogeneous layered structure3A base energy storage ceramic.
SrTiO with heterogeneous layered structure3The dielectric ceramic has dielectric constant of 2532 at room temperature, loss of 0.009, and resistivity of 4.98 × 10 at 1KHz11Omega cm, breakdown field strength of 21kV/mm, and maximum energy storage density of 1.7J/cm3Increased to 9.36J/cm3。
Example 2
Modified SrTiO3The preparation method of the base energy storage medium ceramic comprises the following steps of:
s1, mixing SrCO with the molar ratio of 1:13And TiO2SrTiO made at high temperature3，
S2, mixing 100 parts of SrTiO37 parts of Pb3O43 parts of Bi2O30.8 part of SiO21.2 parts of Al2O3Grinding and mixing uniformly;
s3, calcining for 3 hours at 900 ℃ after uniform mixing to obtain modified SrTiO3And (3) base energy storage medium ceramic.
SrTiO with heterogeneous layered structure3The preparation method of the base energy storage medium ceramic comprises the following steps:
s4, modifying SrTiO obtained in S33Ceramic green ceramic band (A) and TiO based energy storage medium2Raw porcelain band (B), modified SrTiO3Ceramic green porcelain belt of base energy storage medium (A)Stacking according to A-B-A to form a sandwich structure; wherein the modified SrTiO3Ceramic green ceramic band (A) and TiO based energy storage medium2The green tape (B) had a film thickness of 30 μm and was TiO2The thickness of the green ceramic tape (B) accounts for two modified SrTiO310-20% of the total thickness of the base energy storage medium green porcelain tape (A).
Preparation of modified SrTiO by tape casting technology3Ceramic green ceramic tape (A) and TiO based energy storage medium2A raw porcelain band (B) which is formed by a ceramic band,
modified SrTiO3The preparation method of the ceramic green porcelain tape (A) based on the energy storage medium comprises the steps of firstly, obtaining modified SrTiO3 from S33Grinding the base energy storage medium ceramic to obtain modified SrTiO with the average particle size of 0.8um3Based on energy-storing dielectric ceramic powder, modified SrTiO3Pretreating base energy storage dielectric ceramic powder at 135 ℃, and then pretreating SrTiO3Adding the base energy storage medium ceramic powder into a casting medium, ball-milling and uniformly mixing for 10h in a closed environment, defoaming in vacuum, adopting a scraper method for casting molding, adding a binder a on the surface, and drying to obtain the modified SrTiO3The energy-storage medium ceramic green ceramic tape (A) is prepared by mixing a casting medium with a solvent, a binder b, a plasticizer and a dispersant, wherein the solvent is ethanol, the binder a is polyvinyl alcohol, and the addition amount of the polyvinyl alcohol is such that modified SrTiO can be obtained3Ceramic green ceramic band (A) and TiO based energy storage medium2The raw porcelain tapes (B) are bonded together, the binder B is a mixture of ethyl methacrylate and methacrylic acid, and the plasticizer and the dispersant respectively adopt dibutyl phthalate and ammonium polyacrylate in parts by mass, and the modified SrTiO is3The ceramic green porcelain tape (A) of the base energy storage medium comprises 100 parts of modified SrTiO3The energy storage medium comprises base energy storage medium ceramic powder, 11 parts of ethanol, 7.5 parts of binder b, 2.6 parts of dibutyl phthalate and 4 parts of ammonium polyacrylate, wherein the weight percentage of ethyl methacrylate and methacrylic acid in the binder b is 2: 1.
TiO2A process for producing a green tape (B) comprises selecting TiO with an average particle diameter of 0.8um2Powder of TiO2Pretreating the powder at 135 deg.C, and pretreatingTreated TiO2Adding the powder into a casting medium, ball-milling and uniformly mixing for 10h in a closed environment, defoaming in vacuum, carrying out casting molding by adopting a scraper method, adding a binder a on the surface, and drying to obtain TiO2The green ceramic band (B) is prepared from the mixture of solvent, adhesive (B), plasticizer and disperser, the solvent is alcohol, the adhesive (a) is polyvinyl alcohol, and the polyvinyl alcohol is added in such an amount that the modified SrTiO can be obtained3Ceramic green ceramic band (A) and TiO based energy storage medium2Raw porcelain band (B), modified SrTiO3The energy-storage medium ceramic green ceramic tape (A) can be adhered together when being laminated, the binder b is a mixture of ethyl methacrylate and methacrylic acid, and the plasticizer and the dispersant respectively adopt dibutyl phthalate and ammonium polyacrylate in parts by mass, namely TiO2The green ceramic tape (B) comprises 100 parts of modified SrTiO3The energy storage medium comprises base energy storage medium ceramic powder, 11 parts of ethanol, 9.5 parts of binder b, 5.5 parts of dibutyl phthalate and 4 parts of ammonium polyacrylate, wherein the weight percentage of ethyl methacrylate and methacrylic acid in the binder b is 2: 1.
Modified SrTiO3The film thickness of the base energy storage medium ceramic green ceramic tape (A) is 30 microns, and TiO2The green tape (B) had a film thickness of 8 μm.
S5, carrying out cold isostatic pressing on the A-B-A structure to obtain an A-B-A composite biscuit, wherein the pressure intensity is 150MPa in the cold isostatic pressing process, and the pressure maintaining time is 140 seconds;
s6, removing the glue from the composite biscuit, and sintering the composite biscuit for 1.5 hours at the temperature of 1245 ℃ to obtain SrTiO with a heterogeneous layered structure3A base energy storage ceramic. As shown in FIG. 1, the SrTiO is a heterogeneous layered structure3The microstructure diagram of the ceramic of the base energy storage medium.
The SrTiO 3-based energy storage dielectric ceramic with the heterogeneous layered structure has the room-temperature dielectric constant of 2852, the loss of 0.0088 and the resistivity of 5.02 multiplied by 10 under the condition of 1KHz11Omega cm, breakdown field strength of 24kV/mm, and maximum energy storage density of 1.7J/cm3Increased to 9.4J/cm3。
Example 3
Modified SrTiO3The preparation method of the base energy storage medium ceramic comprises the following steps of (by mass portion),the method comprises the following steps:
s1, mixing SrCO with the molar ratio of 1:13And TiO2SrTiO made at high temperature3，
S2, mixing 100 parts of SrTiO38 parts of Pb3O44 parts of Bi2O31 part of SiO21.5 parts of Al2O3Grinding and mixing uniformly;
s3, calcining for 3 hours at 900 ℃ after uniform mixing to obtain modified SrTiO3And (3) base energy storage medium ceramic.
SrTiO with heterogeneous layered structure3The preparation method of the base energy storage medium ceramic comprises the following steps:
s4, modifying SrTiO obtained in S33Ceramic green ceramic band (A) and TiO based energy storage medium2Raw porcelain band (B), modified SrTiO3The ceramic green porcelain tapes (A) of the base energy storage medium are stacked according to A-B-A to form a sandwich structure; wherein the modified SrTiO3Ceramic green ceramic band (A) and TiO based energy storage medium2The green tape (B) had a film thickness of 30 μm and was TiO2The thickness of the green ceramic tape (B) accounts for two modified SrTiO310-20% of the total thickness of the base energy storage medium green porcelain tape (A).
Preparation of modified SrTiO by tape casting technology3Ceramic green ceramic tape (A) and TiO based energy storage medium2A raw porcelain band (B) which is formed by a ceramic band,
modified SrTiO3The preparation method of the ceramic green tape (A) based on the energy storage medium comprises the steps of firstly obtaining the modified SrTiO3Grinding the base energy storage medium ceramic to obtain the modified SrTiO with the average grain diameter of 1um3Based on energy-storing dielectric ceramic powder, modified SrTiO3Pretreating base energy storage dielectric ceramic powder at 140 ℃, and then pretreating SrTiO3Adding the base energy storage medium ceramic powder into a casting medium, ball-milling and uniformly mixing for 12h in a closed environment, defoaming in vacuum, adopting a scraper method for casting molding, adding a binder a on the surface, and drying to obtain the modified SrTiO3The energy-storage medium ceramic green ceramic tape (A) is prepared by mixing a casting medium with a solvent, a binder b, a plasticizer and a dispersant, wherein the solvent is ethanol, and the binder a is polyvinyl alcoholPolyvinyl alcohol is added in an amount to modify SrTiO3Ceramic green ceramic band (A) and TiO based energy storage medium2The raw porcelain tapes (B) are bonded together, the binder B is a mixture of ethyl methacrylate and methacrylic acid, and the plasticizer and the dispersant respectively adopt dibutyl phthalate and ammonium polyacrylate in parts by mass, and the modified SrTiO is3The ceramic green porcelain tape (A) of the base energy storage medium comprises 100 parts of modified SrTiO3The energy storage medium comprises base energy storage medium ceramic powder, 12 parts of ethanol, 8 parts of binder b, 3 parts of dibutyl phthalate and 15 parts of ammonium polyacrylate, wherein the weight percentage of ethyl methacrylate and methacrylic acid in the binder b is 2: 1.
TiO2A process for producing a green tape (B) comprises selecting TiO with an average particle diameter of 1um2Powder of TiO2Pretreating the powder at 140 deg.C, and then adding pretreated TiO2Adding the powder into a casting medium, ball-milling and uniformly mixing for 12h in a closed environment, defoaming in vacuum, carrying out casting molding by adopting a scraper method, adding a binder a on the surface, and drying to obtain TiO2The green ceramic band (B) is prepared from the mixture of solvent, adhesive (B), plasticizer and disperser, the solvent is alcohol, the adhesive (a) is polyvinyl alcohol, and the polyvinyl alcohol is added in such an amount that the modified SrTiO can be obtained3Ceramic green ceramic band (A) and TiO based energy storage medium2Raw porcelain band (B), modified SrTiO3The energy-storage medium ceramic green ceramic tape (A) can be adhered together when being laminated, the binder b is a mixture of ethyl methacrylate and methacrylic acid, and the plasticizer and the dispersant respectively adopt dibutyl phthalate and ammonium polyacrylate in parts by mass, namely TiO2The green ceramic tape (B) comprises 100 parts of modified SrTiO3The energy storage medium comprises base energy storage medium ceramic powder, 12 parts of ethanol, 10 parts of binder b, 6 parts of dibutyl phthalate and 15 parts of ammonium polyacrylate, wherein the weight percentage of ethyl methacrylate and methacrylic acid in the binder b is 2: 1.
Modified SrTiO3The film thickness of the base energy storage medium ceramic green ceramic tape (A) is 32 microns, and TiO2The green tape (B) had a film thickness of 10 μm.
S5, carrying out cold isostatic pressing on the A-B-A structure to obtain an A-B-A composite biscuit, wherein the pressure intensity is 180MPa in the cold isostatic pressing process, and the pressure maintaining time is 180 seconds;
s6, removing the adhesive from the composite biscuit, and sintering at 1270 ℃ for 2 hours to obtain the SrTiO with the heterogeneous layered structure3A base energy storage ceramic.
SrTiO with heterogeneous layered structure3The dielectric ceramic has dielectric constant of 2765 at room temperature, loss of 0.009, and resistivity of 5.2 × 10 at 1KHz11Omega cm, breakdown field strength of 21.8kV/mm, and maximum energy storage density of 1.7J/cm3Increased to 9.38J/cm3。
In examples 1, 2 and 3, the SrTiO 3-based energy storage dielectric ceramic with the heterogeneous layered structure has the room-temperature dielectric constant of 2700 +/-200 and loss at 1KHz<0.01, resistivity>5×1011Omega cm, breakdown field strength>20kV/mm, and the maximum energy storage density of the material is 1.7J/cm3Increased to 9.4J/cm3。
For addition of TiO2Before and after the layer, SrTiO is carried out3The performance of the base energy storage medium ceramics is compared, and the result is shown in table 1,
TABLE 1 addition of TiO2Front and back layers of SrTiO3Comparison table for ceramic performance of base energy storage medium
Wherein, 0% TiO2、10％TiO2、15％TiO2、20％TiO2Are respectively expressed in modified SrTiO3TiO is added into base energy storage medium ceramic2The ratio of layers being different, SrTiO3The base energy storage medium ceramics have different properties.
As can be seen from Table 1, the breakdown field strength of the SrTiO 3-based energy storage dielectric ceramic with the heterogeneous layered structure prepared by the method is equal to that of the ceramic without adding rutile TiO2SrTiO3The ceramic of the basic energy storage medium is improved by 100 percent.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. SrTiO with heterogeneous layered structure3The base energy storage dielectric ceramic is characterized in that: comprising TiO2Green ceramic tape and modified SrTiO3A ceramic green ceramic tape based on an energy storage medium, said TiO2Two modified SrTiO raw porcelain tapes3An interlayer of a base energy storage medium ceramic green ceramic tape.
2. SrTiO with heterogeneous layered structure according to claim 13The base energy storage dielectric ceramic is characterized in that: the modified SrTiO3The base energy storage medium is a raw ceramic tape of 28-32 microns and TiO2The thickness of the green tape is 3-15 microns.
3. SrTiO with heterogeneous layered structure according to claim 1 or 23The base energy storage dielectric ceramic is characterized in that: two of the modified SrTiO3The thickness of the base energy storage medium green ceramic tape is the same, and TiO2The thickness of the raw porcelain band accounts for two modified SrTiO310-20% of the total thickness of the base energy storage medium green ceramic tape.
4. SrTiO with heterogeneous layered structure according to claim 13The base energy storage dielectric ceramic is characterized in that: the SrTiO with the heterogeneous layered structure3The dielectric constant of the base energy storage medium ceramic is 2700 +/-200 at 1KHz and the loss<0.01, resistivity>5X 1011. omega. cm, breakdown field strength>20kV/mm。
5. SrTiO with heterogeneous layered structure according to claim 1 or 43Based on an energy-storing dielectric ceramic, which is characterized in thatCharacterized in that: the SrTiO with the heterogeneous layered structure3The maximum energy storage density of the base energy storage medium ceramic is 1.7J/cm3Increased to 9.4J/cm3。
6. SrTiO with heterogeneous layered structure3The preparation method of the base energy storage medium ceramic is characterized by comprising the following steps: the SrTiO with the heterogeneous layered structure3The base energy storage medium ceramic comprises TiO prepared by adopting a tape casting technology2Green ceramic tape and modified SrTiO according to claim 13Preparation of modified SrTiO by using energy-storage medium ceramic3Based energy storage medium ceramic green ceramic tape, the modified SrTiO3Ceramic green ceramic band and TiO based energy storage medium2Raw porcelain band and modified SrTiO3Sequentially stacking and placing the base energy storage medium ceramic green ceramic tapes to form a sandwich structure, carrying out cold isostatic pressing to obtain a composite biscuit, carrying out binder removal on the composite biscuit, and sintering at the temperature of 1220-3A base energy storage ceramic.
7. SrTiO with heterogeneous layered structure according to claim 63The preparation method of the base energy storage medium ceramic is characterized by comprising the following steps: the pressure in the cold isostatic pressing process is 120-180MPa, and the pressure maintaining time is 90-180 seconds.
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| CN112341191B (en) * | 2020-10-26 | 2022-02-22 | 同济大学 | Lead-free ceramic dielectric with high energy storage density and high energy storage efficiency and preparation method thereof |
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