CN114409402B - Capacitor dielectric porcelain and preparation method thereof - Google Patents

Capacitor dielectric porcelain and preparation method thereof Download PDF

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CN114409402B
CN114409402B CN202210174310.XA CN202210174310A CN114409402B CN 114409402 B CN114409402 B CN 114409402B CN 202210174310 A CN202210174310 A CN 202210174310A CN 114409402 B CN114409402 B CN 114409402B
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capacitor dielectric
coo
porcelain
temperature
crystal phase
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CN114409402A (en
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张晨
王春
卢晶旺
简刚
王锋伟
方响华
朱熠
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Suzhou Pant Piezoelectric Tech Co ltd
Jiangsu University of Science and Technology
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Jiangsu University of Science and Technology
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Abstract

The invention discloses a capacitor dielectric porcelain and a preparation method thereof, and the porcelain comprises the following components of Ba [ (Zr) 0.2 Ti 0.8 ) 1‑ x Ce x ]O 3 MgO and ZnO; the preparation method is to use TiO (OH) 2 As an active matrix, with (CH) 3 COO) 2 Ba、(CH 3 COO) 4 Zr and Ce (NO) 3 ) 4 And drying and calcining the mixture to obtain main crystal phase powder by a liquid phase wrapping method, mixing the main crystal phase powder with MgO and ZnO, grinding, carrying out compression molding and sintering to obtain the capacitor dielectric ceramic material. According to the invention, the porcelain material has the characteristics of high dielectric constant and low dielectric loss through the synergistic effect of the B-site composite perovskite structure main crystal phase and the secondary modifier, and the temperature change rate of the dielectric constant meets the Y5V standard due to the induction of dispersion phase change.

Description

Capacitor dielectric porcelain and preparation method thereof
Technical Field
The invention relates to electronic ceramic and a preparation method thereof, in particular to capacitor dielectric ceramic and a preparation method thereof.
Background
The ceramic capacitor is widely applied to the fields of modern communication, internet of things, consumer electronics, computers, automotive electronics, household appliances and the like. Wherein the Y5V type ceramic capacitor with the capacitance temperature change rate of +22% -82% in a temperature range of-30 ℃ to +85 ℃ is mainly applied to a blocking circuit, a bypass circuit or a decoupling circuit.
Barium zirconate titanate [ Ba (Zr) x Ti 1-x )O 3 ]As barium titanate (BaTiO) 3 ) With barium zirconate (BaZrO) 3 ) The formed solid solution has the characteristics of high dielectricity, adjustable Curie temperature and the like, and becomes one of the dielectric base materials of the ceramic capacitor. However, under the drive of miniaturization and high stability of ceramic capacitors, the multi-parameter synergetic acquisition of barium zirconate titanate-based ceramic dielectric materials with high dielectric constant, low loss and low capacitance-temperature change rate still remains a technical difficulty.
Journal of Applied Physics Letters, vol 91 of 2007, "observer of high specificity in Ho specified BaZr 0.1 Ti 0.9 O 3 ceramics "article discloses a Ba prepared by a solid phase process 1-x Ho x Zr 0.1 Ti 0.9 O 3 (x = 0.01-0.08) ceramic material, which has a dielectric constant at room temperature exceeding 20000 when x =0.02, but has a poor temperature change rate of dielectric constant. Journal of Applied Physics, vol.102, no. 8 of 2007, "Dielectric properties and relaxor modify of ray-earth (La, sm, eu, dy, Y) substitated barium zirconium titanate ceramics" discloses a solid phase process for preparing (Ba 1-x Ln x )Zr 0.2 Ti 0.8-x/4 O 3 (x =0-0.04, ln = La, sm, eu, dy, Y) series ceramic materials in which the loss tangent at x =0.04, ln = La can be as low as 0.00005, but the room temperature dielectric constant is only 650. Journal of electronic Components and materials in 2004, vol.23, no. 10, in the article "study of Properties and Structure of cerium oxide doped barium zirconate titanate ceramics" discloses CeO prepared by solid phase method 2 Doped with Ba (Zr, ti) O 3 The ceramic has a room-temperature dielectric constant of 7193, a temperature change rate of-80.1 to +19.1%, and a room-temperature dielectric loss of 0.0351.
Therefore, there is a need for a barium zirconate titanate based ceramic material having high dielectric constant, low dielectric loss and high dielectric temperature stability.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a capacitor dielectric ceramic material with high dielectric constant, low dielectric loss and dielectric constant temperature change rate meeting the Y5V standard;
the second purpose of the invention is to provide a preparation method of the capacitor dielectric porcelain.
The technical scheme is as follows: the capacitor dielectric porcelain comprises the following components in percentage by mass:
Ba[(Zr 0.2 Ti 0.8 ) 1-x Ce x ]O 3 99.7～99.5wt％
MgO 0.15～0.25wt％
ZnO 0.15～0.25wt％
wherein x = 0.005-0.015.
The preparation method of the capacitor dielectric porcelain comprises the following steps:
(1) Weighing (CH) according to the molar ratio of 1 (0.2-0.2 x) to 0.8-0.8x 3 COO) 2 Ba、(CH 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 Mixing and stirring the materials in water at constant temperature, drying, crushing and calcining to prepare main crystal phase powder;
(2) Adding MgO and ZnO into the main crystal phase powder according to mass percent, grinding, then carrying out compression molding to obtain a green body, and sintering the green body to obtain the capacitor dielectric porcelain.
Wherein in step (1), according to (CH) 3 COO) 2 Mass ratio of Ba to water 1: 3-4 adding (CH) into water 3 COO) 2 Ba、(CH 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 。
In the step (1), the calcining temperature is 1100-1150 ℃, the temperature is kept for 3-4 h, the heating rate is 4-5 ℃/min, and the calcined material is cooled to 850-950 ℃ at the cooling rate of 1-2 ℃/min and then is cooled to room temperature along with the furnace. The temperature reduction rate of the calcination is controlled in a segmented manner so as to fully synthesize the main crystal phase powder and improve the purity of the main crystal phase powder.
Wherein the sintering process in the step (2) comprises the following steps: heating to 1050-1150 ℃ at the speed of 4-5 ℃/min, preserving heat for 1-2 h, heating to 1320-1360 ℃ at the speed of 1-2 ℃/min, sintering, preserving heat for 1-4 h to form porcelain, finally cooling to 1050-1150 ℃ at the speed of 1-2 ℃/min, and cooling to room temperature along with the furnace. The temperature rise and the temperature drop rate of the sintering are controlled in a sectional way, and the multi-section heat preservation is carried out, so that the compact porcelain without macroscopic structure defects is obtained.
Wherein the pressure for compression molding in the step (2) is 5-6 MPa, and the pressure is maintained for 45-60 s. The grinding time is 1-1.5 h.
Wherein in the step (1), the constant temperature is the constant temperature of water bath, and the temperature is 60-80 ℃.
Wherein in the step (1), the stirring is magnetic stirring for 0.5-1 h.
Wherein in the step (1), the drying temperature is 110-120 ℃.
Has the beneficial effects that: compared with the prior art, the invention has the following remarkable effects: 1. through the synergistic effect of the B-site composite perovskite structure main crystal phase and the secondary modifier, the porcelain material not only has the characteristics of high dielectric constant and low dielectric loss, but also has the dielectric constant temperature change rate meeting the Y5V standard due to the induction of dispersion phase change; 2. the porcelain is made of TiO (OH) 2 As an active matrix, with (CH) 3 COO) 2 Ba、(CH 3 COO) 4 Zr and Ce (NO) 3 ) 4 Obtaining B-site composite perovskite structure Ba [ (Zr) by a liquid phase wrapping method for wrapping phase 0.2 Ti 0.8 ) 1-x Ce x ]O 3 The main crystal phase powder not only enables the porcelain to have the characteristics of high dielectric constant and low dielectric loss under the synergistic action of ZnO and MgO serving as secondary modifiers, but also obviously improves the temperature stability of the dielectric constant of the porcelain due to the induction of dispersion phase change, and the temperature change rate of the dielectric constant meets the Y5V standard.
Detailed Description
The present invention is described in further detail below.
Example 1
The main crystal phase powder of the porcelain has a chemical formula as follows: ba [ (Zr) 0.2 Ti 0.8 ) 0.99 Ce 0.01 ]O 3 ，x＝0.01。
The porcelain composition is shown in table 1 below:
TABLE 1 Components and amounts of example 1
Components Powder of main crystal phase MgO ZnO
Content/wt% 99.6 0.2 0.2
The preparation method of the porcelain comprises the following steps:
(1) And (c) in a molar ratio of 1 3 COO) 2 Ba、(CH 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 . Will (CH) 3 COO) 2 Ba is added according to the mass ratio of 1:3.13 dissolving in deionized water and adding successively (CH) 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 Magnetic stirring is carried out for 0.5h in a constant-temperature water bath at 65 ℃, the slurry is dried at 110 ℃, the obtained powder is crushed, the temperature is raised to 1150 ℃ at the speed of 5 ℃/min, the calcination and the heat preservation are carried out for 4h, the powder is cooled to 850 ℃ at the cooling speed of 2 ℃/min, and then the powder is cooled to room temperature along with the furnace to obtain the main crystal phase powder.
(2) Adding MgO and ZnO into the main crystal phase powder according to the components in the table 1, grinding for 1h in an agate mortar, maintaining the pressure for 50s under 6MPa, and carrying out compression molding to obtain a blank; and placing the blank on a ceramic backing plate dispersed with zirconium dioxide padding, heating to 1100 ℃ at the speed of 5 ℃/min, preserving heat for 1h, heating to 1340 ℃ at the speed of 2 ℃/min, sintering and preserving heat for 2h to form porcelain, cooling to 1100 ℃ at the speed of 2 ℃/min, and cooling to room temperature along with a furnace to obtain the capacitor dielectric porcelain, wherein the capacitor dielectric porcelain is well and compactly sintered.
The performance test of the prepared capacitor dielectric ceramic material shows that the room temperature dielectric constant of the capacitor dielectric ceramic material prepared in the embodiment is 2420, the room temperature dielectric loss is 0.0062, and the temperature change rate of the dielectric constant is +6.5% -47.5% within the range of-30 ℃ to +85 ℃.
Example 2
The main crystalline phase powder of the porcelain has a chemical formula as follows: ba [ (Zr) 0.2 Ti 0.8 ) 0.995 Ce 0.005 ]O 3 ，x＝0.005
The porcelain composition is shown in table 2 below:
table 2 example 2 components and amounts thereof
Components Powder of main crystal phase MgO ZnO
Content/wt% 99.6 0.15 0.25
The preparation method of the porcelain comprises the following steps:
(1) And (c) was weighed at a molar ratio of 1 3 COO) 2 Ba、(CH 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 . Will (CH) 3 COO) 2 Ba is in mass ratio1:3.13 dissolving in deionized Water and adding successively (CH) 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 Magnetic stirring is carried out for 0.5h in a constant-temperature water bath at 65 ℃, the slurry is dried at 110 ℃, the obtained powder is crushed, heated to 1150 ℃ at the speed of 5 ℃/min, calcined and kept warm for 4h, cooled to 850 ℃ at the cooling speed of 2 ℃/min, and then cooled to room temperature along with the furnace, and the main crystal phase powder is obtained.
(2) Adding MgO and ZnO into the powder of the main crystal phase according to the components in the table 2, grinding for 1h in an agate mortar, maintaining the pressure for 50s at 6MPa, and carrying out compression molding to obtain a blank; and placing the blank on a ceramic backing plate dispersed with zirconium dioxide padding, heating to 1100 ℃ at the speed of 5 ℃/min, preserving heat for 1h, heating to 1340 ℃ at the speed of 2 ℃/min, sintering and preserving heat for 2h to form porcelain, cooling to 1100 ℃ at the speed of 2 ℃/min, and cooling to room temperature along with a furnace to obtain the capacitor dielectric porcelain, wherein the capacitor dielectric porcelain is well and compactly sintered.
The performance test of the prepared capacitor dielectric ceramic shows that the room temperature dielectric constant of the capacitor dielectric ceramic prepared in the embodiment is 2347, the room temperature dielectric loss is 0.0059, and the temperature change rate of the dielectric constant is +9.6% -45.5% within the range of-30 ℃ to +85 ℃.
Example 3
The main crystal phase powder of the porcelain has a chemical formula as follows: ba [ (Zr) 0.2 Ti 0.8 ) 0.985 Ce 0.015 ]O 3 ，x＝0.015。
The porcelain composition is shown in table 3 below:
table 3 components and amounts thereof of example 3
Components Powder of main crystal phase MgO ZnO
Content/wt% 99.65 0.2 0.15
The preparation method of the porcelain comprises the following steps:
(1) Weighed (CH) 3 COO) 2 Ba、(CH 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 . Will (CH) 3 COO) 2 Ba is added according to the mass ratio of 1:3.13 dissolving in deionized water and adding successively (CH) 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 Magnetic stirring is carried out for 0.5h in a constant-temperature water bath at 65 ℃, the slurry is dried at 110 ℃, the obtained powder is crushed, heated to 1150 ℃ at the speed of 5 ℃/min, calcined and kept warm for 4h, cooled to 850 ℃ at the cooling speed of 2 ℃/min, and then cooled to room temperature along with the furnace, and the main crystal phase powder is obtained.
(2) Adding MgO and ZnO into the main crystal phase powder according to the components in the table 3, grinding for 1h in an agate mortar, maintaining the pressure for 50s under 6MPa, and carrying out compression molding to obtain a blank; and placing the blank on a ceramic backing plate dispersed with zirconium dioxide padding, heating to 1100 ℃ at the speed of 5 ℃/min, preserving heat for 1h, heating to 1340 ℃ at the speed of 2 ℃/min, sintering and preserving heat for 2h to form porcelain, cooling to 1100 ℃ at the speed of 2 ℃/min, and cooling to room temperature along with a furnace to obtain the capacitor dielectric porcelain, wherein the capacitor dielectric porcelain is well and compactly sintered.
As can be seen from the performance detection of the prepared capacitor dielectric ceramic, the room temperature dielectric constant of the capacitor dielectric ceramic prepared in the embodiment is 2432, and the room temperature dielectric loss is 0.0063, and the temperature change rate of the dielectric constant is +16.9% -51.7% within the range of-30 ℃ to +85 ℃.
Example 4
The main crystal phase powder of the porcelain has a chemical formula as follows: ba [ (Zr) 0.2 Ti 0.8 ) 0.985 Ce 0.015 ]O 3 ，x＝0.015。
The porcelain composition is shown in table 4 below:
table 4 components and amounts thereof of example 4
Components Powder of main crystal phase MgO ZnO
Content/wt% 99.5 0.25 0.25
The preparation method of the porcelain comprises the following steps:
(1) Weighed (CH) 3 COO) 2 Ba、(CH 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 . Will (CH) 3 COO) 2 Ba is added according to the mass ratio of 1:4 dissolved in deionized water and added successively (CH) 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 Magnetically stirring the mixture for 1 hour in a constant-temperature water bath at the temperature of 80 ℃, drying the slurry at the temperature of 120 ℃, crushing the obtained powder, heating the powder to 1150 ℃ at the speed of 5 ℃/min, calcining, keeping the temperature for 4 hours, cooling the powder to 950 ℃ at the cooling speed of 2 ℃/min, and cooling the powder to room temperature along with the furnace to obtain the main crystal phase powder.
(2) Adding MgO and ZnO into the main crystal phase powder according to the components in the table 4, grinding the mixture in an agate mortar for 1.5h, maintaining the pressure for 60s under 6MPa, and carrying out compression molding to obtain a blank; and placing the blank on a ceramic backing plate dispersed with zirconium dioxide padding, heating to 1150 ℃ at the speed of 5 ℃/min, preserving heat for 2h, heating to 1360 ℃ at the speed of 2 ℃/min, sintering, preserving heat for 4h to form porcelain, cooling to 1150 ℃ at the speed of 2 ℃/min, and cooling to room temperature along with a furnace to obtain the capacitor dielectric porcelain, wherein the capacitor dielectric porcelain is well sintered and compact.
As can be seen from the performance detection of the prepared capacitor dielectric ceramic, the room temperature dielectric constant of the capacitor dielectric ceramic prepared in the embodiment is 2513, and the room temperature dielectric loss is 0.0062, and the temperature change rate of the dielectric constant is +15.6% -50.5% within the range of-30 ℃ to +85 ℃.
Example 5
The main crystal phase powder of the porcelain has a chemical formula as follows: ba [ (Zr) 0.2 Ti 0.8 ) 0.995 Ce 0.005 ]O 3 ，x＝0.005。
The porcelain composition is shown in table 5 below:
table 5 components and amounts thereof of example 5
Components Powder of main crystal phase MgO ZnO
Content/wt% 99.7 0.15 0.15
The preparation method of the porcelain comprises the following steps:
(1) And (c) was weighed at a molar ratio of 1 3 COO) 2 Ba、(CH 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 . Will (CH) 3 COO) 2 Ba is added according to the mass ratio of 1:3 dissolved in deionized water and successively added (CH) 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 Magnetically stirring the mixture in a constant-temperature water bath at 60 ℃ for 0.5h, drying the slurry at 110 ℃, crushing the obtained powder, heating the powder to 1100 ℃ at the speed of 4 ℃/min, calcining and preserving heat for 3h, cooling the powder to 850 ℃ at the cooling speed of 1 ℃/min, and cooling the powder to room temperature along with the furnace to obtain the main crystal phase powder.
(2) Adding MgO and ZnO into the main crystal phase powder according to the components in the table 5, grinding for 1h in an agate mortar, maintaining the pressure for 45s under 5MPa, and carrying out compression molding to obtain a blank; and placing the blank on a ceramic backing plate dispersed with zirconium dioxide padding, heating to 1050 ℃ at a speed of 4 ℃/min, preserving heat for 1h, heating to 1320 ℃ at a speed of 1 ℃/min, sintering and preserving heat for 1h to form porcelain, cooling to 1050 ℃ at a speed of 1 ℃/min, and cooling to room temperature along with a furnace to obtain the capacitor dielectric porcelain, wherein the capacitor dielectric porcelain is well sintered and compact.
The performance test of the prepared capacitor dielectric ceramic shows that the room temperature dielectric constant of the capacitor dielectric ceramic prepared in the embodiment is 2393, the room temperature dielectric loss is 0.0061, and the temperature change rate of the dielectric constant is +8.3% -42.7% within the range of-30 ℃ to +85 ℃.
Comparative example 1
The main crystal phase powder of the porcelain has a chemical formula as follows: ba [ (Zr) 0.2 Ti 0.8 ) 0.98 Ce 0.02 ]O 3 ，x＝0.02。
The porcelain composition is shown in table 6 below:
TABLE 6 COMPARATIVE EXAMPLE 1 Components and amounts thereof
Components Powder of main crystal phase MgO ZnO
Content/wt% 99.6 0.2 0.2
The preparation method of the porcelain comprises the following steps:
(1) Weighed in a molar ratio of 1 3 COO) 2 Ba、(CH 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 . Will (CH) 3 COO) 2 Ba is mixed according to the mass ratio of 1:3.13 dissolving in deionized water and adding successively (CH) 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 Magnetic stirring is carried out for 0.5h in a constant-temperature water bath at 65 ℃, the slurry is dried at 110 ℃, the obtained powder is crushed, the temperature is raised to 1150 ℃ at the speed of 5 ℃/min, the calcination and the heat preservation are carried out for 4h, the powder is cooled to 850 ℃ at the cooling speed of 2 ℃/min, and then the powder is cooled to room temperature along with the furnace to obtain the main crystal phase powder.
(2) Adding MgO and ZnO into the main crystal phase powder according to the components in the table 6, grinding for 1h in an agate mortar, maintaining the pressure for 50s under 6MPa, and carrying out compression molding to obtain a blank; and placing the blank on a ceramic backing plate dispersed with zirconium dioxide padding, heating to 1100 ℃ at the speed of 5 ℃/min, preserving heat for 1h, heating to 1340 ℃ at the speed of 2 ℃/min, sintering and preserving heat for 2h to form porcelain, cooling to 1100 ℃ at the speed of 2 ℃/min, and cooling to room temperature along with a furnace to obtain the capacitor dielectric porcelain, wherein the capacitor dielectric porcelain is well and compactly sintered.
As can be seen from performance detection of the prepared capacitor dielectric ceramic, the room-temperature dielectric constant of the capacitor dielectric ceramic prepared in the embodiment is 2428, and the room-temperature dielectric loss is 0.0066, but the maximum value of the corresponding dielectric constant at the Curie temperature is remarkably increased, and the temperature change rate of the dielectric constant is +40.9% -70.0% within the range of-30 ℃ to +85 ℃.
Comparative example 2
The main crystal phase powder of the porcelain has a chemical formula as follows: ba (Zr) 0.2 Ti 0.8 )O 3 ，x＝0。
The porcelain composition is shown in table 7 below:
TABLE 7 COMPARATIVE EXAMPLE 2 Components and their amounts
Components Powder of main crystal phase MgO ZnO
Content/wt% 99.6 0.2 0.2
The preparation method of the porcelain comprises the following steps:
(1) And (CH) in a molar ratio of 1 3 COO) 2 Ba、(CH 3 COO) 4 Zr and TiO (OH) 2 . Will (CH) 3 COO) 2 Ba is added according to the mass ratio of 1:3.13 dissolving in deionized water and adding successively (CH) 3 COO) 4 Zr and TiO (OH) 2 Magnetic stirring is carried out for 0.5h in a constant-temperature water bath at 65 ℃, the slurry is dried at 110 ℃, the obtained powder is crushed, heated to 1150 ℃ at the speed of 5 ℃/min, calcined and kept warm for 4h, cooled to 850 ℃ at the cooling speed of 2 ℃/min, and then cooled to room temperature along with the furnace, and the main crystal phase powder is obtained.
(2) Adding MgO and ZnO into the main crystal phase powder according to the components in the table 7, grinding for 1h in an agate mortar, maintaining the pressure for 50s under 6MPa, and carrying out compression molding to obtain a blank; and placing the blank on a ceramic backing plate dispersed with zirconium dioxide padding, heating to 1100 ℃ at the speed of 5 ℃/min, preserving heat for 1h, heating to 1340 ℃ at the speed of 2 ℃/min, sintering and preserving heat for 2h to form porcelain, cooling to 1100 ℃ at the speed of 2 ℃/min, and cooling to room temperature along with a furnace to obtain the capacitor dielectric porcelain, wherein the capacitor dielectric porcelain is well and compactly sintered.
As can be seen from the performance test of the prepared capacitor dielectric ceramic, the dielectric loss at room temperature of the capacitor dielectric ceramic prepared in the embodiment is 0.0058, the temperature change rate of the dielectric constant is +12.3% -44.1% within the range of-30 ℃ to +85 ℃, but the dielectric constant at room temperature is only 1990 because the spontaneous polarization intensity of the unit cell is low.
Comparative example 3
The main crystal phase powder of the porcelain has a chemical formula as follows: ba (Zr) 0.2 Ti 0.8 )O 3 ，x＝0。
The porcelain composition is shown in table 8 below:
TABLE 8 COMPARATIVE EXAMPLE 3 Components and their amounts
Components Powder of main crystal phase MgO ZnO
Content/wt% 100 0 0
The preparation method of the porcelain comprises the following steps:
(1) And (CH) in a molar ratio of 1 3 COO) 2 Ba、(CH 3 COO) 4 Zr and TiO (OH) 2 . Will (CH) 3 COO) 2 Ba is added according to the mass ratio of 1:3.5 dissolving in deionized water and adding successively (CH) 3 COO) 4 Zr and TiO (OH) 2 Magnetically stirring the mixture in a constant-temperature water bath at 65 ℃ for 0.5h, drying the slurry at 110 ℃, crushing the obtained powder, heating the powder to 1150 ℃ at the speed of 5 ℃/min, calcining, keeping the temperature for 4h, and cooling the powder to room temperature along with a furnace to obtain the main crystal phase powder.
(2) Grinding the main crystal phase powder in an agate mortar for 1h, maintaining the pressure for 50s under 6MPa, and carrying out compression molding to obtain a blank; and (3) placing the blank on a ceramic base plate dispersed with zirconium dioxide padding, heating to 1100 ℃ at the speed of 5 ℃/min, preserving heat for 1h, heating to 1340 ℃ at the speed of 2 ℃/min, sintering, preserving heat for 2h, and cooling to room temperature along with a furnace, wherein the surface of the prepared sample has a large number of holes and has no obvious shrinkage compared with the blank.
Comparative example 4
The main crystal phase powder of the porcelain has a chemical formula as follows: ba (Zr) 0.2 Ti 0.8 )O 3 ，x＝0。
The porcelain composition is shown in table 9 below:
TABLE 9 COMPARATIVE EXAMPLE 4 COMPONENTS AND ITS CONTENT
Components Powder of main crystal phase MgO ZnO
Content/wt% 100 0 0
The preparation method of the porcelain comprises the following steps:
(1) And (CH) in a molar ratio of 1 3 COO) 2 Ba、(CH 3 COO) 4 Zr and TiO (OH) 2 . Will (CH) 3 COO) 2 Ba is added according to the mass ratio of 1:3.5 dissolving in deionized Water and adding successively (CH) 3 COO) 4 Zr and TiO (OH) 2 Magnetic stirring is carried out for 0.5h in a constant-temperature water bath at 65 ℃, the slurry is dried at 110 ℃, the obtained powder is crushed, heated to 1150 ℃ at the speed of 5 ℃/min, calcined and kept for 4h, cooled to 1000 ℃ at the cooling speed of 2 ℃/min, and then cooled to room temperature along with the furnace, and the main crystal phase powder is obtained.
(2) Grinding the main crystal phase powder in an agate mortar for 1h, maintaining the pressure at 6MPa for 50s, and carrying out compression molding to obtain a blank; placing the blank on a ceramic backing plate dispersed with zirconium dioxide padding, heating to 1100 ℃ at the speed of 5 ℃/min, preserving heat for 1h, heating to 1340 ℃ at the speed of 2 ℃/min, sintering and preserving heat for 2h, cooling to 1100 ℃ at the speed of 2 ℃/min, and cooling to room temperature along with the furnace, wherein a small number of holes are formed in the surface of the prepared sample, and the sample has no obvious shrinkage compared with the blank.
Comparative example 5
The main crystal phase powder of the porcelain has a chemical formula as follows: ba (Zr) 0.2 Ti 0.8 )O 3 ，x＝0。
The porcelain composition is shown in table 10 below:
TABLE 10 comparative example 5 Components and amounts thereof
Components Powder of main crystal phase MgO ZnO
Content/wt% 100 0 0
The preparation method of the porcelain comprises the following steps:
(1) And (CH) in a molar ratio of 1 3 COO) 2 Ba、(CH 3 COO) 4 Zr and TiO (OH) 2 . Will (CH) 3 COO) 2 Ba is added according to the mass ratio of 1:3.5 dissolving in deionized water and adding successively (CH) 3 COO) 4 Zr and TiO (OH) 2 Magnetic stirring is carried out for 0.5h in a constant-temperature water bath at 65 ℃, the slurry is dried at 110 ℃, the obtained powder is crushed, heated to 1150 ℃ at the speed of 5 ℃/min, calcined and kept for 4h, cooled to 1000 ℃ at the cooling speed of 2 ℃/min, and then cooled to room temperature along with the furnace, and the main crystal phase powder is obtained.
(2) Grinding the main crystal phase powder in an agate mortar for 1h, maintaining the pressure for 50s under 6MPa, and carrying out compression molding to obtain a blank; and (3) placing the blank on a ceramic base plate dispersed with zirconium dioxide padding, heating to 1100 ℃ at the speed of 5 ℃/min, preserving heat for 1h, heating to 1340 ℃ at the speed of 2 ℃/min, sintering, preserving heat for 2h, and cooling to room temperature along with a furnace, wherein holes exist on the surface of the prepared sample, and the sample is uneven and has no obvious shrinkage compared with the blank.

Claims (10)

1. The capacitor dielectric porcelain is characterized by comprising the following components in percentage by mass:
Ba[(Zr 0.2 Ti 0.8 ) 1-x Ce x ]O 3 99.7~99.5 wt%
MgO 0.15~0.25 wt%
ZnO 0.15~0.25 wt%
wherein x =0.005 to 0.015.
2. A method for preparing a dielectric porcelain for capacitors as claimed in claim 1, comprising the steps of:
(1) Weighing (CH) according to the molar ratio of 1 (0.2-0.2 x) to 0.8-0.8x 3 COO) 2 Ba、(CH 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 Mixing and stirring the materials in water at constant temperature, drying, crushing and calcining the materials to obtain main crystal phase powder;
(2) Adding MgO and ZnO into the main crystal phase powder according to mass percent, grinding, then carrying out compression molding to obtain a green body, and sintering the green body to obtain the capacitor dielectric porcelain.
3. The method for preparing a capacitor dielectric porcelain according to claim 2, wherein in the step (1), the Component (CH) is 3 COO) 2 Mass ratio of Ba to water 1:3 to 4 (CH) is added to water 3 COO) 2 Ba、(CH 3 COO) 4 Zr、TiO(OH) 2 And Ce (NO) 3 ) 4 。
4. The method for preparing the capacitor dielectric porcelain according to claim 2, wherein in the step (1), the ceramic is cooled to 850 to 950 ℃ at a cooling rate of 1 to 2 ℃/min after calcination, and then is cooled to room temperature along with a furnace.
5. The preparation method of the capacitor dielectric ceramic material as claimed in claim 2, wherein in the step (1), the calcining temperature is 1100-1150 ℃, the heat preservation time is 3-4 h, and the heating rate is 4-5 ℃/min.
6. The method for preparing the capacitor dielectric ceramic material as claimed in claim 2, wherein in the step (2), the temperature is reduced to 1050 to 1150 ℃ at 1 to 2 ℃/min after sintering, and then the ceramic material is cooled to room temperature along with a furnace.
7. The method for preparing the capacitor dielectric ceramic material according to claim 2, wherein in the step (2), the sintering is carried out by heating to 1050 to 1150 ℃ at 4 to 5 ℃/min and keeping the temperature for 1 to 2h, and then heating to 1320 to 1360 ℃ at 1 to 2 ℃/min and keeping the temperature for 1 to 4h to form the ceramic.
8. The method for preparing the capacitor dielectric porcelain according to claim 2, wherein in the step (1), the constant temperature is a water bath constant temperature, and the temperature is 60-80 ℃.
9. The preparation method of the capacitor dielectric porcelain according to claim 2, wherein in the step (1), the stirring is magnetic stirring for 0.5 to 1h.
10. The method for preparing the capacitor dielectric porcelain according to claim 2, wherein in the step (1), the drying temperature is 110 to 120 ℃.
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