CN111620683B - High-energy-storage-density ceramic block with core-shell structure and preparation method thereof - Google Patents

High-energy-storage-density ceramic block with core-shell structure and preparation method thereof Download PDF

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CN111620683B
CN111620683B CN202010421698.XA CN202010421698A CN111620683B CN 111620683 B CN111620683 B CN 111620683B CN 202010421698 A CN202010421698 A CN 202010421698A CN 111620683 B CN111620683 B CN 111620683B
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张洪军
唐晓慧
柯华
曹璐
罗蕙佳代
田晶鑫
吴春龙
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Harbin Institute of Technology
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Abstract

A high energy storage density ceramic block with a core-shell structure and a preparation method thereof relate to a high energy storage density ferroelectric ceramic and a preparation method thereof. The invention aims to solve the problem of low energy storage density of the existing bismuth ferrite-based ceramic. The chemical general formula of the high energy storage density ceramic block with the core-shell structure is alpha Bi1‑x‑ yRxByFeO3‑βBaTiO3. The method comprises the following steps: firstly, preparing alpha Bi1‑x‑ yRxByFeO3‑βBaTiO3Ceramic mixed powderA body; secondly, granulating; thirdly, tabletting and removing glue; fourthly, sintering; fifthly, quenching. Alpha Bi prepared by the invention1‑x‑yRxByFeO3‑βBaTiO3The high energy storage density ceramic block body has a core-shell structure, the ceramic with the structure has high energy storage density theoretically, and the method is suitable for preparing the high energy storage density ceramic block body.

Description

High-energy-storage-density ceramic block with core-shell structure and preparation method thereof
Technical Field
The invention relates to a ferroelectric ceramic with high energy storage density and a preparation method thereof.
Background
Bismuth ferrite (BiFeO)3) Is a single-phase multiferroic material at room temperature, and theoretically, the spontaneous polarization value of the material can approach 100 mu C/cm2But the synthesis of the material is easy to generate a heterogeneous phase, and the leakage current is very large; barium titanate (BaTiO)3) Has good ferroelectricity, residual polarization value and BiFeO3Relatively small. Therefore, BiFeO is adopted3Adding nano BaTiO3The method achieves the aim of high energy storage density, but the bismuth ferrite-based ceramic prepared by the existing method still has the problem of low energy storage density, so the invention adopts the traditional solid phase reaction method to prepare the bismuth ferrite-based ceramic with high energy storage density.
Disclosure of Invention
The invention aims to solve the problem of low energy storage density of the existing bismuth ferrite-based ceramic, and provides a high energy storage density ceramic block with a core-shell structure and a preparation method thereof.
The chemical general formula of the high energy storage density ceramic block with the core-shell structure is alpha Bi1-x-yRxByFeO3-βBaTiO3Wherein, 0<x≤0.2，0<y≤0.05；α＝0.3～0.8；Beta is 1-alpha, and x and y are mole fractions; r is neodymium element, lanthanum element or cerium element, B is samarium element, europium element, gadolinium element or dysprosium element.
A preparation method of a high energy storage density ceramic block with a core-shell structure is completed according to the following steps:
firstly, preparing alpha Bi1-x-yRxByFeO3-βBaTiO3Ceramic mixed powder:
firstly, weighing materials:
according to the chemical formula alpha Bi1-x-yRxByFeO3-βBaTiO3Weighing bismuth oxide, iron oxide, R oxide and B oxide, wherein 0<x≤0.2，0<y is less than or equal to 0.05, and x and y are mole fractions;
weighing bismuth oxide again:
the molar ratio of the bismuth oxide weighed in the first step to the bismuth oxide weighed in the first step is (0.01-0.1): 1;
thirdly, weighing BaTiO according to the molar ratio of alpha to beta3Nano ceramic powder, wherein alpha is 0.3-0.8, beta is 1-alpha;
fourthly, weighing the bismuth oxide, the iron oxide, the R oxide, the B oxide and the BaTiO which are obtained in the first step and the first step3Adding nano ceramic powder into a ball milling tank, adding a ball milling medium, namely absolute ethyl alcohol and grinding balls, and mixing the grinding balls by using a high-energy planetary ball mill to obtain a mixture I;
fifthly, drying the mixture I to obtain a dried mixture;
heating the dried mixture from room temperature to 700-800 ℃ at the heating rate of 1-5 ℃/min, preserving the heat at the temperature of 700-800 ℃ for 3-6 h, and cooling to room temperature along with the furnace to obtain the alpha Bi1-x-yRxByFeO3-βBaTiO3Ceramic mixed powder;
secondly, granulation:
alpha Bi1-x-yRxByFeO3-βBaTiO3Grinding the ceramic mixed powder in an agate mortar, and adding a binderGranulating the aqueous solution, and sieving the granulated aqueous solution through a sieve of 150 meshes to 200 meshes to obtain mixed powder with the particle size of less than 150 meshes to 200 meshes;
alpha Bi described in step two1-x-yRxByFeO3-βBaTiO3The mass ratio of the ceramic mixed powder to the binder in the binder aqueous solution is (19-49): 1;
thirdly, tabletting and removing glue:
firstly, drying mixed powder with the particle size of less than 150-200 meshes in an oven at the temperature of 50-90 ℃ for 3-5 min, adding the dried mixed powder into a stainless steel mold with the diameter of 10-50 mm, and maintaining the pressure at 150-200 MPa for 1-3 min to obtain a prepressed block;
secondly, crushing the pre-pressed blocks, grinding, and finally screening by a 100-200-mesh screen to obtain screened powder; placing the sieved powder into a stainless steel mold with the diameter of 5-30 mm, and maintaining the pressure at 550-700 MPa for 3-5 min to obtain a wafer with the diameter of 5-30 mm and the thickness of 0.5-2 mm;
thirdly, carrying out glue removal on the wafer with the diameter of 5-30 mm and the thickness of 0.5-2 mm to obtain a ceramic biscuit after glue removal;
fourthly, sintering:
heating the ceramic biscuit subjected to the binder removal to 750-950 ℃ in an oxygen atmosphere, preserving heat, and then cooling to room temperature to obtain a ceramic block;
fifthly, quenching:
putting the ceramic block obtained in the fourth step into a tubular furnace, heating the tubular furnace from room temperature to 500-800 ℃, preserving heat at 500-800 ℃, directly taking out the ceramic block after heat preservation, placing the ceramic block in air, and cooling the ceramic block to room temperature to obtain the alpha Bi with the core-shell structure1-x-yRxByFeO3-βBaTiO3High energy storage density ceramic blocks.
The principle and the advantages of the invention are as follows:
firstly, the alpha Bi with the core-shell structure prepared by the invention1-x-yRxByFeO3-βBaTiO3The high energy storage density ceramic block has a core-shell structure; ceramics of this structureHaving the characteristics of a ferroelectric switch;
secondly, the alpha Bi with the core-shell structure prepared by the invention1-x-yRxByFeO3-βBaTiO3The high energy storage density ceramic block body has a core-shell structure, and the ceramic with the structure has high energy storage density theoretically, so that the aim of high energy storage density is fulfilled;
thirdly, the alpha Bi with the core-shell structure prepared by the invention1-x-yRxByFeO3-βBaTiO3The effective energy storage density of the high energy storage density ceramic block body is 3.08J/cm3～3.64J/cm3(ii) a The energy storage efficiency is 80.2-81.4%.
The method is suitable for preparing the ceramic block with high energy storage density.
Drawings
FIG. 1 shows 0.5Bi with core-shell structure prepared in example one0.88Nd0.1Sm0.02FeO3-0.5BaTiO3XRD pattern of the high energy storage density ceramic block;
FIG. 2 is a hysteresis loop spectrum, wherein the first is a hysteresis loop spectrum of the ceramic block obtained in the fourth step of the example measured at a field strength of 200kV/cm, and the second is 0.5Bi having a core-shell structure obtained in the fifth step of the example0.88Nd0.1Sm0.02FeO3-0.5BaTiO3Measuring a hysteresis loop map of the high energy storage density ceramic block under the field intensity of 200 kV/cm;
FIG. 3 shows 0.5Bi with core-shell structure prepared in example one0.88Nd0.1Sm0.02FeO3-0.5BaTiO3A back-scattered electron image of an SEM of a high energy storage density ceramic block;
FIG. 4 shows the hysteresis loop of the ceramic at different quenching temperatures at a field strength of 200kV/cm, wherein: 0.5Bi having a core-shell structure prepared in example II at a quenching temperature of 600 ℃0.88Nd0.1Sm0.02FeO3-0.5BaTiO3The electric hysteresis loop of the high energy storage density ceramic block body measured under the field intensity of 200kV/cm is 0.5Bi with the core-shell structure prepared in the first embodiment when the quenching temperature is 700 DEG C0.88Nd0.1Sm0.02FeO3-0.5BaTiO3The electric hysteresis loop of the high energy storage density ceramic block body measured under the field intensity of 200kV/cm, and 0.5Bi with the core-shell structure prepared in the third embodiment when the quenching temperature is 800 DEG C0.88Nd0.1Sm0.02FeO3-0.5BaTiO3And (3) measuring the electric hysteresis loop of the high energy storage density ceramic block under the field intensity of 200 kV/cm.
Detailed Description
The technical scheme of the invention comprises but is not limited to the following specific embodiments and any combination of the specific embodiments.
The first embodiment is as follows: the chemical general formula of the high energy storage density ceramic block with the core-shell structure is alpha Bi1-x-yRxByFeO3-βBaTiO3Wherein, 0<x≤0.2，0<y is less than or equal to 0.05; alpha is 0.3-0.8; beta is 1-alpha, and x and y are mole fractions; r is neodymium element, lanthanum element or cerium element, B is samarium element, europium element, gadolinium element or dysprosium element.
The second embodiment is as follows: the embodiment is a preparation method of a high energy storage density ceramic block with a core-shell structure, which is completed according to the following steps:
firstly, preparing alpha Bi1-x-yRxByFeO3-βBaTiO3Ceramic mixed powder:
firstly, weighing materials:
according to the chemical formula alpha Bi1-x-yRxByFeO3-βBaTiO3Weighing bismuth oxide, iron oxide, R oxide and B oxide, wherein 0<x≤0.2，0<y is less than or equal to 0.05, and x and y are mole fractions;
weighing bismuth oxide again:
the molar ratio of the bismuth oxide weighed in the first step to the bismuth oxide weighed in the first step is (0.01-0.1): 1;
thirdly, weighing BaTiO according to the molar ratio of alpha to beta3Nano ceramic powder, wherein alpha is 0.3-0.8, beta is 1-alpha;
fourthly, weighing the bismuth oxide, the iron oxide, the R oxide, the B oxide and the BaTiO which are obtained in the first step and the first step3Adding nano ceramic powder into a ball milling tank, adding a ball milling medium, namely absolute ethyl alcohol and grinding balls, and mixing the grinding balls by using a high-energy planetary ball mill to obtain a mixture I;
fifthly, drying the mixture I to obtain a dried mixture;
heating the dried mixture from room temperature to 700-800 ℃ at the heating rate of 1-5 ℃/min, preserving the heat at the temperature of 700-800 ℃ for 3-6 h, and cooling to room temperature along with the furnace to obtain the alpha Bi1-x-yRxByFeO3-βBaTiO3Ceramic mixed powder;
secondly, granulation:
alpha Bi1-x-yRxByFeO3-βBaTiO3Grinding the ceramic mixed powder in an agate mortar, adding a binder aqueous solution for granulation, and sieving by a sieve of 150-200 meshes to obtain the mixed powder with the particle size of less than 150-200 meshes;
alpha Bi described in step two1-x-yRxByFeO3-βBaTiO3The mass ratio of the ceramic mixed powder to the binder in the binder aqueous solution is (19-49): 1;
thirdly, tabletting and removing glue:
firstly, drying mixed powder with the particle size of less than 150-200 meshes in an oven at the temperature of 50-90 ℃ for 3-5 min, adding the dried mixed powder into a stainless steel mold with the diameter of 10-50 mm, and maintaining the pressure at 150-200 MPa for 1-3 min to obtain a prepressed block;
secondly, crushing the pre-pressed blocks, grinding, and finally screening by a 100-200-mesh screen to obtain screened powder; placing the sieved powder into a stainless steel mold with the diameter of 5-30 mm, and maintaining the pressure at 550-700 MPa for 3-5 min to obtain a wafer with the diameter of 5-30 mm and the thickness of 0.5-2 mm;
thirdly, carrying out glue removal on the wafer with the diameter of 5-30 mm and the thickness of 0.5-2 mm to obtain a ceramic biscuit after glue removal;
fourthly, sintering:
heating the ceramic biscuit subjected to the binder removal to 750-950 ℃ in an oxygen atmosphere, preserving heat, and then cooling to room temperature to obtain a ceramic block;
fifthly, quenching:
putting the ceramic block obtained in the fourth step into a tubular furnace, heating the tubular furnace from room temperature to 500-800 ℃, preserving heat at 500-800 ℃, directly taking out the ceramic block after heat preservation, placing the ceramic block in air, and cooling the ceramic block to room temperature to obtain the alpha Bi with the core-shell structure1-x-yRxByFeO3-βBaTiO3High energy storage density ceramic blocks.
The principle and advantages of the embodiment are as follows:
first, α Bi having a core-shell structure prepared in this embodiment1-x-yRxByFeO3-βBaTiO3The high energy storage density ceramic block has a core-shell structure; the ceramic of this structure has the characteristics of a ferroelectric switch;
second, α Bi having a core-shell structure prepared in this embodiment1-x-yRxByFeO3-βBaTiO3The high energy storage density ceramic block body has a core-shell structure, and the ceramic with the structure has high energy storage density theoretically, so that the aim of high energy storage density is fulfilled;
third, α Bi having a core-shell structure prepared in this embodiment1-x-yRxByFeO3-βBaTiO3The effective energy storage density of the high energy storage density ceramic block body is 3.08J/cm3～3.64J/cm3(ii) a The energy storage efficiency is 80.2-81.4%.
The embodiment is suitable for preparing the ceramic block with high energy storage density.
The third concrete implementation mode: the present embodiment is different from the second embodiment in that: the bismuth oxide in the first step and the second step is bismuth oxide; the oxide R in the first step is neodymium oxide, lanthanum oxide or cerium oxide. The other steps are the same as those in the second embodiment.
The fourth concrete implementation mode: the present embodiment differs from the second to third embodiments in that: the oxide B is samarium oxide, europium oxide, gadolinium oxide or dysprosium oxide; the iron oxide in the first step is ferric oxide. The other steps are the same as those in the second to third embodiments.
The fifth concrete implementation mode: the second to fourth embodiments are different from the first to fourth embodiments in that: step one the BaTiO mentioned3The grain size of the nano ceramic powder is less than 100 nm; the rotating speed of the ball mill in the first step is 250 r/min-350 r/min, the ball-material ratio is (10-15): 1, and the ball milling time is 20 h-30 h; the drying temperature in the first step is 60-80 ℃, and the drying time is 20-24 h. The other steps are the same as those in the second to fourth embodiments.
The sixth specific implementation mode: the second to fifth embodiments are different from the first to fifth embodiments in that: step two, dropwise adding the aqueous solution of the binder to the alpha Bi in several times1-x-yRxByFeO3-βBaTiO3Dripping 3-10 drops of the adhesive into the ceramic mixed powder every time, continuously grinding for 3-5 min after dripping each time, then dripping the adhesive for the next time until the dripping of the adhesive aqueous solution is finished, and sieving the adhesive aqueous solution through a sieve of 150-200 meshes to obtain the mixed powder with the particle size of less than 150-200 meshes; the aqueous solution of the binder is a polyvinyl alcohol aqueous solution, and the mass fraction of the polyvinyl alcohol aqueous solution is 5-10%. The other steps are the same as those in the second to fifth embodiments.
The seventh embodiment: the present embodiment differs from one of the second to sixth embodiments in that: and the diameter of the stainless steel die in the third step is smaller than or equal to that of the stainless steel die in the third step. The other steps are the same as in embodiments two to six.
The specific implementation mode is eight: the second embodiment differs from the first embodiment in that: thirdly, the glue discharging process comprises the following steps: firstly, heating a wafer with the diameter of 5-30 mm and the thickness of 0.5-2 mm from room temperature to 150-300 ℃ at the heating rate of 0.5-1 ℃/min, then heating the wafer from 150-300 ℃ to 450-550 ℃ at the heating rate of 0.5-1 ℃/min, then preserving heat at 450-550 ℃ for 1-2 h, and finally cooling the wafer to room temperature along with a furnace to obtain the ceramic biscuit after glue discharging. The other steps are the same as those in the second to seventh embodiments.
The specific implementation method nine: the second to eighth differences from the first embodiment are as follows: in the fourth step, the ceramic biscuit after the glue removal is firstly heated to 750-950 ℃ at the heating rate of 5-30 ℃/min under the oxygen atmosphere, then the temperature is kept at 750-950 ℃ for 2-6 h, and finally the temperature is reduced from 750-950 ℃ to room temperature at the cooling rate of 5-30 ℃/min, thus obtaining the ceramic block. The other steps are the same as those in the second to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from the second to ninth embodiments in that: and fifthly, the temperature rise rate of the tubular furnace is 5-30 ℃/min, and the heat preservation time is 10-40 min at 500-800 ℃. The other steps are the same as in the second to ninth embodiments.
The following specific examples are given by way of illustration of the embodiments of the present invention and are intended to provide detailed illustrations and specific procedures, but the scope of the present invention is not limited to the following examples.
The first embodiment is as follows: the chemical general formula of the high energy storage density ceramic block with the core-shell structure is alpha Bi1-x- yRxByFeO3-βBaTiO3Wherein x is 0.1 and y is 0.02; α ═ β ═ 0.5, and x and y are mole fractions; r is Nd element, B is Sm element, namely the chemical general formula of the high energy storage density ceramic block with the core-shell structure prepared by the embodiment is 0.5Bi0.88Nd0.1Sm0.02FeO3-0.5BaTiO3The specific preparation method comprises the following steps:
first, prepare 0.5Bi0.88Nd0.1Sm0.02FeO3-0.5BaTiO3Ceramic mixed powder;
firstly, weighing materials:
according to the chemical formula 0.5Bi0.88Nd 0.1Sm0.02FeO3-0.5BaTiO3Weighing oxidationBismuth, iron oxide, neodymium oxide, and samarium oxide;
weighing bismuth oxide again:
the molar ratio of the bismuth oxide weighed in the first step to the bismuth oxide weighed in the first step is 0.03: 1;
③ according to Bi0.88Nd 0.1Sm0.02FeO3With BaTiO3Is 1:1, weighing BaTiO3Nano ceramic powder;
step one the BaTiO mentioned3The grain size of the nano ceramic powder is less than 100 nm;
fourthly, weighing the bismuth oxide, the ferric oxide, the neodymium oxide, the samarium oxide and the BaTiO which are obtained in the first step and the first step3Adding nano ceramic powder into a ball milling tank, adding a ball milling medium, namely absolute ethyl alcohol and grinding balls, and mixing the grinding balls by using a high-energy planetary ball mill to obtain a mixture I;
the rotating speed of the ball mill in the first step is 300r/min, the ball-material ratio is 13:1, and the ball milling time is 24 hours; fifthly, drying the mixture I at 80 ℃ for 24 hours to obtain a dried mixture;
heating the dried mixture from room temperature to 750 ℃ at the heating rate of 2 ℃/min, preserving the heat at 750 ℃ for 3 hours, and then cooling the mixture to the room temperature along with the furnace to obtain 0.5Bi0.88Nd0.1Sm0.02FeO3-0.5BaTiO3Ceramic mixed powder;
secondly, granulation:
0.5Bi0.88Nd0.1Sm0.02FeO3-0.5BaTiO3Grinding the ceramic mixed powder in an agate mortar, and dropwise adding the polyvinyl alcohol aqueous solution to 0.5Bi in several times0.88Nd0.1Sm0.02FeO3-0.5BaTiO3Dripping 5 drops of the mixed powder into the ceramic mixed powder every time, continuously grinding for 4min after dripping is finished every time, dripping the mixed powder for the next time until the dripping of the polyvinyl alcohol aqueous solution is finished, and sieving the mixed powder with a sieve of 150 meshes to 200 meshes to obtain the mixed powder with the particle size of less than 150 meshes to 200 meshes;
0.5Bi described in step two0.88Nd0.1Sm0.02FeO3-0.5BaTiO3The mass ratio of the ceramic mixed powder to the polyvinyl alcohol in the polyvinyl alcohol aqueous solution is 30: 1;
the mass fraction of the polyvinyl alcohol aqueous solution in the second step is 5%;
thirdly, tabletting and removing glue:
firstly, drying mixed powder with the particle size of less than 150 meshes to 200 meshes in an oven at the temperature of 80 ℃ for 5min, adding the dried mixed powder into a stainless steel mold with the diameter of 20mm, and maintaining the pressure at 150MPa for 3min to obtain a pre-pressed block body;
secondly, crushing the pre-pressed blocks, grinding, and finally screening by a 100-200-mesh screen to obtain screened powder; placing the sieved powder into a stainless steel mold with the diameter of 10mm, and maintaining the pressure at 600MPa for 4min to obtain a wafer with the diameter of 10mm and the thickness of 1 mm;
thirdly, carrying out glue removal on the wafer with the diameter of 10mm and the thickness of 1mm to obtain a ceramic biscuit after glue removal;
thirdly, the glue discharging process comprises the following steps: firstly, heating a wafer with the diameter of 10mm and the thickness of 1mm from room temperature to 300 ℃ at the heating rate of 1 ℃/min, then heating from 300 ℃ to 550 ℃ at the heating rate of 0.5 ℃/min, then preserving heat at 550 ℃ for 1h, and finally cooling to room temperature along with a furnace to obtain a ceramic biscuit after glue discharging;
fourthly, sintering:
heating the ceramic biscuit after the binder removal from room temperature to 850 ℃ at the heating rate of 10 ℃/min under the oxygen atmosphere, then preserving the heat for 3h at 850 ℃, and then cooling from 850 ℃ to room temperature at the cooling rate of 10 ℃/min to obtain a ceramic block;
fifthly, quenching:
putting the ceramic block obtained in the fourth step into a tube furnace, heating the tube furnace from room temperature to 700 ℃ at the heating rate of 10 ℃/min, preserving the heat at 700 ℃ for 15min, directly taking out the tube furnace after heat preservation, placing the tube furnace in air, and cooling the tube furnace to room temperature to obtain the 0.5Bi with the core-shell structure0.88Nd0.1Sm0.02FeO3-0.5BaTiO3High energy storage density ceramic blocks.
FIG. 1 is a schematic view of an embodimentExample one prepared 0.5Bi having a core-shell Structure0.88Nd0.1Sm0.02FeO3-0.5BaTiO3XRD pattern of the high energy storage density ceramic block;
as can be seen from fig. 1; all phases are perovskite phases without impurity phases, which indicates that the rare earth elements are completely doped with 0.5Bi0.88Nd0.1Sm0.02FeO3-0.5BaTiO3In ceramics.
FIG. 2 is a hysteresis loop spectrum, wherein the first is a hysteresis loop spectrum of the ceramic block obtained in the fourth step of the example measured at a field strength of 200kV/cm, and the second is 0.5Bi having a core-shell structure obtained in the fifth step of the example0.88Nd0.1Sm0.02FeO3-0.5BaTiO3Measuring a hysteresis loop map of the high energy storage density ceramic block under the field intensity of 200 kV/cm;
as can be seen from FIG. 2, curve 1 is the ceramic mass obtained without the step five quenching and the effective energy storage density is 2.88J/cm3(ii) a Curve 2 is 0.5Bi having a core-shell structure obtained by quenching in the fifth step (quenching temperature of 700 ℃ C.)0.88Nd0.1Sm0.02FeO3-0.5BaTiO3The high energy storage density ceramic block has an effective energy storage density of 3.33J/cm3. From the above data, it can be understood that the effective energy storage density of the sample is improved after the sample is subjected to the quenching process.
FIG. 3 shows 0.5Bi with core-shell structure prepared in example one0.88Nd0.1Sm0.02FeO3-0.5BaTiO3A back-scattered electron image of an SEM of a high energy storage density ceramic block;
as is clear from the backscattered electron image of the SEM of FIG. 3, 0.5Bi prepared in example one0.88Nd0.1Sm0.02FeO3-0.5BaTiO3The ceramic sample is of a core-shell structure (circle mark), wherein the core is BaTiO3The shell is Bi0.88Nd0.1Sm0.02FeO3。
Example two: the present embodiment is different from the first embodiment in that: putting the ceramic block obtained in the fourth step into a tubular furnace, and then putting the ceramic block into the tubular furnaceHeating the tube furnace from room temperature to 600 ℃ at a heating rate of 10 ℃/min, then preserving heat at 600 ℃ for 15min, directly taking out the tube furnace after heat preservation, placing the tube furnace in air, and cooling the tube furnace to room temperature to obtain 0.5Bi with a core-shell structure0.88Nd0.1Sm0.02FeO3-0.5BaTiO3High energy storage density ceramic blocks. Other steps and parameters are the same as those in the first embodiment.
Example three: the present embodiment is different from the first embodiment in that: putting the ceramic block obtained in the fourth step into a tubular furnace, heating the tubular furnace from room temperature to 800 ℃ at a heating rate of 10 ℃/min, then preserving heat at 800 ℃ for 15min, directly taking out the ceramic block after heat preservation, and cooling the ceramic block in the air to room temperature to obtain 0.5Bi with the core-shell structure0.88Nd0.1Sm0.02FeO3-0.5BaTiO3High energy storage density ceramic blocks. Other steps and parameters are the same as those in the first embodiment.
FIG. 4 shows the hysteresis loop of the ceramic at different quenching temperatures at a field strength of 200kV/cm, wherein: 0.5Bi having a core-shell structure prepared in example II at a quenching temperature of 600 ℃0.88Nd0.1Sm0.02FeO3-0.5BaTiO3The electric hysteresis loop of the high energy storage density ceramic block body measured under the field intensity of 200kV/cm is 0.5Bi with the core-shell structure prepared in the first embodiment when the quenching temperature is 700 DEG C0.88Nd0.1Sm0.02FeO3-0.5BaTiO3The electric hysteresis loop of the high energy storage density ceramic block body measured under the field intensity of 200kV/cm, and 0.5Bi with the core-shell structure prepared in the third embodiment when the quenching temperature is 800 DEG C0.88Nd0.1Sm0.02FeO3-0.5BaTiO3The electric hysteresis loop is measured by the high energy storage density ceramic block under the field intensity of 200 kV/cm;
as can be seen from FIG. 4, 0.5Bi having a core-shell structure prepared in example two at a quenching temperature of 600 deg.C0.88Nd0.1Sm0.02FeO3-0.5BaTiO3The effective energy storage density of the high energy storage density ceramic block is 2.69J/cm3(ii) a 0.5Bi with core-shell structure prepared in the first embodiment at the quenching temperature of 700 DEG C0.88Nd0.1Sm0.02FeO3-0.5BaTiO3The effective energy storage density of the high energy storage density ceramic block body is 3.33J/cm3(ii) a 0.5Bi with core-shell structure prepared in the third embodiment at the quenching temperature of 800 DEG C0.88Nd0.1Sm0.02FeO3-0.5BaTiO3The effective energy storage density of the high energy storage density ceramic block body is 3.08J/cm3Specific numerical values thereof are shown in table 1.
TABLE 1
Quenching temperature (. degree. C.) Pmax(μC/cm2) Pr(μC/cm2) ΔP Energy storage Density (J/cm)3)
600 35.95 3.13 31.62 2.69
700 48.72 3.92 45.76 3.33
800 44.05 3.90 40.15 3.08

Claims (10)

1. A high energy storage density ceramic block with a core-shell structure is characterized in that the chemical general formula of the high energy storage density ceramic block with the core-shell structure is alpha Bi1-x-yRxByFeO3-βBaTiO3Wherein, BaTiO3As a nucleus, Bi1-x-yRxByFeO3Is a shell, 0<x≤0.2，0<y is less than or equal to 0.05; alpha is 0.3-0.8; beta is 1-alpha, and x and y are mole fractions; r is neodymium element, lanthanum element or cerium element, B is samarium element, europium element, gadolinium element or dysprosium element.
2. The method for preparing the high energy storage density ceramic block with the core-shell structure according to claim 1, wherein the method for preparing the high energy storage density ceramic block with the core-shell structure is completed according to the following steps:
firstly, preparing alpha Bi1-x-yRxByFeO3-βBaTiO3Ceramic mixed powder:
firstly, weighing materials:
according to the chemical formula alpha Bi1-x-yRxByFeO3-βBaTiO3Weighing bismuth oxide, iron oxide, R oxide and B oxide, wherein 0<x≤0.2，0<y is less than or equal to 0.05, and x and y are mole fractions;
weighing bismuth oxide again:
the molar ratio of the bismuth oxide weighed in the first step to the bismuth oxide weighed in the first step is (0.01-0.1): 1;
thirdly, weighing BaTiO according to the molar ratio of alpha to beta3Nano ceramic powder, wherein alpha is 0.3-0.8, beta is 1-alpha;
④、weighing bismuth oxide, iron oxide, R oxide, B oxide and BaTiO in the first step and the second step3Adding nano ceramic powder into a ball milling tank, adding a ball milling medium, namely absolute ethyl alcohol and grinding balls, and mixing the grinding balls by using a high-energy planetary ball mill to obtain a mixture I;
fifthly, drying the mixture I to obtain a dried mixture;
heating the dried mixture from room temperature to 700-800 ℃ at the heating rate of 1-5 ℃/min, preserving the heat at the temperature of 700-800 ℃ for 3-6 h, and cooling to room temperature along with the furnace to obtain the alpha Bi1-x-yRxByFeO3-βBaTiO3Ceramic mixed powder;
secondly, granulation:
alpha Bi1-x-yRxByFeO3-βBaTiO3Grinding the ceramic mixed powder in an agate mortar, adding a binder aqueous solution for granulation, and sieving by a sieve of 150-200 meshes to obtain the mixed powder with the particle size of less than 150-200 meshes;
alpha Bi described in step two1-x-yRxByFeO3-βBaTiO3The mass ratio of the ceramic mixed powder to the binder in the binder aqueous solution is (19-49): 1;
thirdly, tabletting and removing glue:
firstly, drying mixed powder with the particle size of less than 150-200 meshes in an oven at the temperature of 50-90 ℃ for 3-5 min, adding the dried mixed powder into a stainless steel mold with the diameter of 10-50 mm, and maintaining the pressure at 150-200 MPa for 1-3 min to obtain a prepressed block;
secondly, crushing the pre-pressed blocks, grinding, and finally screening by a 100-200-mesh screen to obtain screened powder; placing the sieved powder into a stainless steel mold with the diameter of 5-30 mm, and maintaining the pressure at 550-700 MPa for 3-5 min to obtain a wafer with the diameter of 5-30 mm and the thickness of 0.5-2 mm;
thirdly, carrying out glue removal on the wafer with the diameter of 5-30 mm and the thickness of 0.5-2 mm to obtain a ceramic biscuit after glue removal;
fourthly, sintering:
heating the ceramic biscuit subjected to the binder removal to 750-950 ℃ in an oxygen atmosphere, preserving heat, and then cooling to room temperature to obtain a ceramic block;
fifthly, quenching:
putting the ceramic block obtained in the fourth step into a tubular furnace, heating the tubular furnace from room temperature to 500-800 ℃, preserving heat at 500-800 ℃, directly taking out the ceramic block after heat preservation, placing the ceramic block in air, and cooling the ceramic block to room temperature to obtain the alpha Bi with the core-shell structure1-x-yRxByFeO3-βBaTiO3High energy storage density ceramic blocks.
3. The method for preparing the high energy storage density ceramic block with the core-shell structure according to claim 2, wherein the bismuth oxide in the first step and the first step is bismuth oxide; the oxide R in the first step is neodymium oxide, lanthanum oxide or cerium oxide.
4. The method according to claim 2, wherein the oxide B in step one is samarium oxide, europium oxide, gadolinium oxide or dysprosium oxide; the iron oxide in the first step is ferric oxide.
5. The method for preparing high energy storage density ceramic block with core-shell structure according to claim 2, wherein the BaTiO in the first step3The grain size of the nano ceramic powder is less than 100 nm; the rotating speed of the ball mill in the first step is 250 r/min-350 r/min, the ball-material ratio is (10-15): 1, and the ball milling time is 20 h-30 h; the drying temperature in the first step is 60-80 ℃, and the drying time is 20-24 h.
6. The method for preparing high energy storage density ceramic block with core-shell structure according to claim 2, wherein the aqueous solution of the binder is added to the α Bi in step two by drops1-x-yRxByFeO3-βBaTiO3Dripping 3-10 drops of the adhesive into the ceramic mixed powder every time, continuously grinding for 3-5 min after dripping each time, then dripping the adhesive for the next time until the dripping of the adhesive aqueous solution is finished, and sieving the adhesive aqueous solution through a sieve of 150-200 meshes to obtain the mixed powder with the particle size of less than 150-200 meshes; the aqueous solution of the binder is a polyvinyl alcohol aqueous solution, and the mass fraction of the polyvinyl alcohol aqueous solution is 5-10%.
7. The method for preparing a ceramic block with a core-shell structure and a high energy storage density according to claim 2, wherein the diameter of the stainless steel mold in the third step is less than or equal to that of the stainless steel mold in the third step.
8. The method for preparing the high energy storage density ceramic block body with the core-shell structure according to claim 2, wherein the glue removing process in the third step is as follows: firstly, heating a wafer with the diameter of 5-30 mm and the thickness of 0.5-2 mm from room temperature to 150-300 ℃ at the heating rate of 0.5-1 ℃/min, then heating the wafer from 150-300 ℃ to 450-550 ℃ at the heating rate of 0.5-1 ℃/min, preserving heat at 450-550 ℃ for 1-2 h, and finally cooling the wafer to room temperature along with a furnace to obtain the ceramic biscuit after glue discharging.
9. The method for preparing a high energy storage density ceramic block with a core-shell structure according to claim 2, characterized in that in the fourth step, the ceramic biscuit after binder removal is heated to 750-950 ℃ at a heating rate of 5-30 ℃/min under an oxygen atmosphere, then the temperature is kept at 750-950 ℃ for 2-6 h, and finally the temperature is reduced from 750-950 ℃ to room temperature at a cooling rate of 5-30 ℃/min, so as to obtain the ceramic block.
10. The method for preparing the high energy storage density ceramic block with the core-shell structure according to claim 2, wherein the temperature rise rate of the fifth-step tubular furnace is 5 ℃/min to 30 ℃/min, and the holding time at 500 ℃ to 800 ℃ is 10min to 40 min.
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