CN116041060B - Base metal pulse energy storage ceramic dielectric material, ceramic capacitor and preparation method thereof - Google Patents

Base metal pulse energy storage ceramic dielectric material, ceramic capacitor and preparation method thereof Download PDF

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CN116041060B
CN116041060B CN202310076689.5A CN202310076689A CN116041060B CN 116041060 B CN116041060 B CN 116041060B CN 202310076689 A CN202310076689 A CN 202310076689A CN 116041060 B CN116041060 B CN 116041060B
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energy storage
base metal
pulse energy
dielectric material
ultrasonic
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CN116041060A (en
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陈本夏
林柄锋
郑冬建
罗培福
陈永虹
宋运雄
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Fujian Torch Electron Technology Co ltd
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Abstract

The invention discloses a base metal pulse energy storage ceramic dielectric material, a ceramic capacitor and a preparation method thereof, wherein the ceramic dielectric material comprises the following raw materials in percentage by weight: [ a wt% (Ba) 1‑ x Ca x )(Ti 1‑y Zr y )O 3 +b wt％(SiO 2 ‑Al 2 O 3 )]Wherein, (Ba) 1‑x Ca x )(Ti 1‑y Zr y )O 3 SiO as a main matrix 2 ‑Al 2 O 3 As sintering auxiliary agent, x is more than or equal to 0.4 and less than or equal to 0.7,0.4, y is more than or equal to 0.7, a is more than or equal to 85 and less than or equal to 98, b is more than or equal to 2 and less than or equal to 15, a and b are mass percentages of main matrix and sintering auxiliary agent respectively, and mesoporous alumina SiO doped with silicon dioxide is distributed on the surface of the main matrix 2 ‑Al 2 O 3 And (3) nanoparticles. The particle size of the ceramic dielectric material prepared by combining a solid phase method with an ultrasonic-assisted sol-gel method is 300-500nm, and the ceramic dielectric material can be co-fired with a base metal electrode, has good suitability, and simultaneously has the advantages of low dielectric loss, high dielectric constant, excellent charge and discharge performance, good temperature stability and the like.

Description

Base metal pulse energy storage ceramic dielectric material, ceramic capacitor and preparation method thereof
Technical Field
The invention relates to the field of ceramic capacitors, in particular to a base metal pulse energy storage ceramic dielectric material, a ceramic capacitor and a preparation method thereof.
Background
With the development of technical fields such as electronic information, aerospace, automobile electronics and the like, electronic equipment, an ignition device circuit, an electronic fuse and the like gradually tend to be miniaturized, integrated and portable, so that higher requirements are put on the pulse energy storage device. The Pd/Ag inner electrode used by the conventional pulse capacitor has high price, so that the development of the base metal pulse energy storage ceramic dielectric material has important significance.
Chip multilayer ceramic capacitors (Multilayer Ceramic Capacitor, MLCCs) are common ceramic dielectric capacitors that meet the quality requirements of the capacitances required for high power, high withstand voltage electronic equipment, and there is a current trend to develop chip capacitors with higher currents, higher withstand voltages, higher power and low equivalent series resistance.
Several classes of energy storage dielectric ceramic materials are currently of greatest interest, such as ferroelectric BaTiO 3 The base ceramic has low energy storage efficiency of the capacitor due to low breakdown strength and high remnant polarization, so that how to modify the base ceramic to improve the energy storage performance of the pulse energy storage ceramic dielectric material is an important difficult problem. In addition, the method for preparing the pulse energy storage ceramic dielectric material is such as the traditional solid phase method, the granularity and the grain size distribution of the main matrix powder are difficult to control, and the sintering temperature is high, so that the development of a preparation method capable of effectively controlling the granularity and the grain size distribution of the main matrix powder and reducing the sintering temperature is also important.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a base metal pulse energy storage ceramic dielectric material, a ceramic capacitor and a preparation method thereof. The pulse energy storage ceramic dielectric material which has uniform particle size distribution and can be co-fired with the base metal electrode is prepared by combining a solid phase method with an ultrasonic auxiliary sol-gel method, and meanwhile, the advantages of lower dielectric loss, higher dielectric constant, excellent charge and discharge performance, good temperature stability and the like are considered.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the base metal pulse energy storage ceramic dielectric material comprises the following components in percentage by weight: [ a ]
wt％(Ba 1-x Ca x )(Ti 1-y Zr y )O 3 +b wt％(SiO 2 -Al 2 O 3 )]Wherein, (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 SiO as a main matrix 2 -Al 2 O 3 As sintering aids, x is more than or equal to 0.4 and less than or equal to 0.7,0.4, y is more than or equal to 0.7, a is more than or equal to 85 and less than or equal to 98, b is more than or equal to 2 and less than or equal to 15, and a and b are mass percentages of the main matrix and the sintering aids respectively.
Preferably, the raw material component of the main matrix is BaCO 3 、CaCO 3 、TiO 2 And ZrO(s) 2 。
Preferably, the raw material component of the sintering aid is C 8 H 20 O 4 Si and C 9 H 21 AlO 3 。
Preferably, the sintering aid is SiO synthesized by combining a solid phase method with an ultrasonic-assisted sol-gel method and using a PEO-PPO-PEO triblock copolymer as a template agent 2 Doped mesoporous Al 2 O 3 Nanoparticles and are distributed on the surface of the host matrix.
A preparation method of a base metal pulse energy storage ceramic dielectric material comprises the following steps:
step 1, according to the chemical formula (Ba 1-x Ca x )(Ti 1-y Zr y )O 3 Wherein x is more than or equal to 0.4 and less than or equal to 0.7,0.4, y is more than or equal to 0.7, a is more than or equal to 85 and less than or equal to 98, b is more than or equal to 2 and less than or equal to 15, and BaCO is used as the catalyst 3 、CaCO 3 、TiO 2 And ZrO(s) 2 Preparing raw materials, ball milling, drying, crushing and presintering by using deionized water as a dispersion medium to obtain (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 Powder;
step 2, step (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 Ball milling, stoving and sieving to obtain (Ba) 1-x Ca x )(Ti 1- y Zr y )O 3 Precursor powder;
step 3, according to SiO 2 -Al 2 O 3 Is prepared from C 9 H 21 AlO 3 Ultrasonic dispersion in isopropanol;
step 4, adding the PEO-PPO-PEO triblock copolymer into the mixed solution of absolute ethyl alcohol and acetic acid, performing ultrasonic dispersion until the PEO-PPO-PEO triblock copolymer is dissolved, and then adding (Ba 1-x Ca x )(Ti 1-y Zr y )O 3 Precursor powder, controlling the pH value to be about 0.5-1.5, and continuing ultrasonic treatment to obtain suspension;
step 5, slowly dripping the solution obtained in the step 3 into the suspension, and uniformly dispersing and mixing by ultrasonic to obtain a mixed solution;
step 6, C 8 H 20 O 4 Si is dissolved in absolute ethyl alcohol, then is slowly dripped into the mixed solution, and the ultrasonic dispersion reaction is continued;
and 7, aging, drying, crushing and sieving the solution obtained in the step 6 at room temperature to obtain the base metal pulse energy storage ceramic dielectric material.
Preferably, the weight ratio of deionized water to materials in the ball milling process of the step 1 and the step 2 is 2:1, the ball milling medium adopted is zirconia balls, and the weight ratio of the ball milling medium to the materials is 5:1, the rotating speed is 400-600rpm/min, and the ball milling time is 2-6h.
Preferably, the temperature of the drying in the step 1 and the step 2 is 120-150 ℃, and the drying time is 4-12h; the presintering temperature in the step 1 is 900-1100 ℃, and the heat preservation time is 2-4h.
Preferably, the aging temperature in the step 7 is 25 ℃, and the aging time is 6-12 hours; the drying temperature is 60-80 ℃, and the drying time is 6-12h.
Preferably, the power of ultrasonic dispersion is 300-600W, the temperature of ultrasonic dispersion in the step 3 is 25-35 ℃, and the time of ultrasonic dispersion is 10-20min; in the step 4, the volume ratio of the absolute ethyl alcohol to the acetic acid is 100:1, a step of; the ultrasonic dispersion time is 10-30min; and the ultrasonic dispersion time in the step 5 and the step 6 is 0.5h-2h.
A method for preparing a ceramic capacitor based on the base metal pulse energy storage ceramic dielectric material comprises the following steps:
step 1, sieving a base metal pulse energy storage ceramic dielectric material, adding 8-10wt% of paraffin wax for granulation, and pressing into a green body under 5-8 Mpa;
Step 2, the green body is processed in H 2 Heating to 500 ℃ at a speed of 10 ℃/min in a reducing atmosphere, preserving heat for 2-4h, then heating to 1150-1250 ℃, preserving heat for 2-6h, and sintering to obtain a ceramic sheet;
and 3, sintering the ceramic chip to infiltrate the copper electrode to prepare the ceramic capacitor.
A ceramic capacitor prepared based on the base metal pulse energy storage ceramic dielectric material.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts a mode of combining a solid phase method and an ultrasonic-assisted sol-gel method, and utilizes triblock copolymer P123 as a template agent to effectively synthesize SiO with a mesoporous structure 2 The doped alumina can accelerate the hydrolysis process of Al precursor by ultrasonic assistance, shorten the synthesis reaction time, control the pore size distribution of mesoporous alumina, coat the mesoporous alumina on the surface of a main matrix of a medium material in the form of nanometer small particles in an ultrasonic environment, and control the granularity and the particle size distribution of main matrix powder, wherein the particle size is mainly distributed between 300 nm and 500 nm.
(2) The base metal pulse energy storage medium ceramic material obtained by the invention has uniform particle size distribution, room temperature dielectric constant of more than 150 and loss tangent value tg delta of less than 10 -4 The compressive strength can reach more than 8kV/mm, and the volume resistivity at normal temperature is more than 1.0X10 12 Omega cm, volume resistivity at 125 deg.C > 1.0X10 11 Omega cm, is suitable for producing multilayer ceramic dielectric capacitors with large capacity and high energy storage efficiency.
(3) The base metal pulse energy storage medium ceramic material obtained by the application replaces Pd/Ag inner electrodes with high price with base metal, thereby meeting the requirement of reducing the production cost to a great extent and laying a foundation for researching and developing the pulse energy storage medium material which is independently controllable, low-temperature and resistant to reduction sintering.
Drawings
The accompanying drawings are included to provide a further understanding of the embodiments and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments and together with the description serve to explain the principles of the application. Many of the intended advantages of the other embodiments will be readily appreciated as they become better understood by reference to the following detailed description.
FIG. 1 is a graph showing the rate of change of capacitance versus temperature of ceramic capacitors obtained in examples 1-4 of the present application;
fig. 2 is a SEM result graph of the base metal pulse energy storage ceramic dielectric materials obtained in examples 3 and 4 of the present application, wherein fig. 2 (a) is a SEM result graph of the base metal pulse energy storage ceramic dielectric material obtained in example 3, and fig. 2 (b) is a SEM result graph of the base metal pulse energy storage ceramic dielectric material obtained in example 4.
Detailed Description
The application is described in further detail below with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the application and are not limiting of the application. It should be noted that, for convenience of description, only the portions related to the present application are shown in the drawings.
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
The embodiment of the application provides a base metal pulse energy storage ceramic dielectric material, which comprises the following components in percentage by weight: [ a wt% (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 +b wt％(SiO 2 -Al 2 O 3 )]Wherein, (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 SiO as a main matrix 2 -Al 2 O 3 As sintering aids, x is more than or equal to 0.4 and less than or equal to 0.7,0.4, y is more than or equal to 0.7, a is more than or equal to 85 and less than or equal to 98, b is more than or equal to 2 and less than or equal to 15, and a and b are mass percentages of the main matrix and the sintering aids respectively.
Specifically, the raw material component of the main matrix is BaCO 3 、CaCO 3 、TiO 2 And ZrO(s) 2 . Sintering aidThe raw material component is C 8 H 20 O 4 Si and C 9 H 21 AlO 3 。
Specifically, the sintering aid is SiO synthesized by combining a solid phase method with an ultrasonic-assisted sol-gel method and using a PEO-PPO-PEO triblock copolymer as a template agent 2 Doped mesoporous Al 2 O 3 Nanoparticles distributed on the surface of the host matrix.
The base metal pulse energy storage ceramic dielectric material prepared by the invention has uniform granularity and particle size distribution, replaces Pd/Ag inner electrodes with high price with base metal electrodes, meets the requirement of reducing the production cost to a great extent, and has the advantages of low dielectric loss, higher dielectric constant, excellent charge and discharge performance, good temperature stability and the like. By reacting BaTiO 3 The base ceramic is modified to enable the base ceramic to show excellent temperature performance and energy storage property; linear dielectric materials such as TiO 2 Etc., low dielectric constant but high breakdown electric field, and good temperature and frequency stability; zrO with high insulation 2 Introduced into ceramic dielectric material, uniformly distributed ZrO 2 The inter-crystalline phase is beneficial to charge transmission between the crystal grains and the crystal boundary, and the electric field strength is improved; in addition, al also having high insulation 2 O 3 The addition of the ceramic material can also effectively reduce the sintering temperature of the ceramic material and improve the dielectric breakdown strength. The elements such as Ca, bi and the like are introduced into the system to reduce dielectric loss and improve discharge efficiency.
The embodiment of the invention also provides a preparation method of the base metal pulse energy storage ceramic dielectric material, which comprises the following steps:
Step 1, according to the chemical formula (Ba 1-x Ca x )(Ti 1-y Zr y )O 3 Wherein x is more than or equal to 0.4 and less than or equal to 0.7,0.4, y is more than or equal to 0.7, a is more than or equal to 85 and less than or equal to 98, b is more than or equal to 2 and less than or equal to 15, and BaCO is used as the catalyst 3 、CaCO 3 、TiO 2 And ZrO(s) 2 Preparing raw materials, ball milling, drying, crushing and presintering by using deionized water as a dispersion medium to obtain (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 Powder;
step 2, step (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 Ball milling, stoving and sieving to obtain (Ba) 1-x Ca x )(Ti 1- y Zr y )O 3 Precursor powder;
step 3, according to SiO 2 -Al 2 O 3 Is prepared from C 9 H 21 AlO 3 Ultrasonic dispersion in isopropanol;
step 4, adding the PEO-PPO-PEO triblock copolymer into the mixed solution of absolute ethyl alcohol and acetic acid, performing ultrasonic dispersion until the PEO-PPO-PEO triblock copolymer is dissolved, and then adding (Ba 1-x Ca x )(Ti 1-y Zr y )O 3 Precursor powder, controlling the pH value to be about 0.5-1.5, and continuing ultrasonic treatment to obtain suspension;
step 5, slowly dripping the solution obtained in the step 3 into the suspension, and uniformly dispersing and mixing by ultrasonic to obtain a mixed solution;
step 6, C 8 H 20 O 4 Si is dissolved in absolute ethyl alcohol, then is slowly dripped into the mixed solution, and the ultrasonic dispersion reaction is continued;
and 7, aging, drying, crushing and sieving the solution obtained in the step 6 at room temperature to obtain the base metal pulse energy storage ceramic dielectric material.
Specifically, in the ball milling process of step 1 and step 2, the weight ratio of deionized water to materials is 2:1, the ball milling medium adopted is zirconia balls, and the weight ratio of the ball milling medium to the materials is 5:1, the rotating speed is 400-600rpm/min, and the ball milling time is 2-6h.
Specifically, the temperature of the drying in the step 1 and the step 2 is 120-150 ℃, and the drying time is 4-12 hours; the presintering temperature in the step 1 is 900-1100 ℃, and the heat preservation time is 2-4h.
Specifically, the aging temperature in the step 7 is 25 ℃, and the aging time is 6-12 hours; the drying temperature is 60-80 ℃, and the drying time is 6-12h.
Specifically, the power of ultrasonic dispersion is 300-600W, the temperature of ultrasonic dispersion in the step 3 is 25-35 ℃, and the time of ultrasonic dispersion is 10-20min; in the step 4, the volume ratio of the absolute ethyl alcohol to the acetic acid is 100:1, a step of; the ultrasonic dispersion time is 10-30min; and the ultrasonic dispersion time in the step 5 and the step 6 is 0.5h-2h.
The embodiment of the invention also provides a method for preparing the ceramic capacitor based on the base metal pulse energy storage ceramic dielectric material, which comprises the following steps:
(1) Sieving a base metal pulse energy storage ceramic dielectric material, adding 8-10wt% of paraffin wax for granulating, and pressing into a green body under 5-8 Mpa;
(2) Green body at H 2 Heating to 500 ℃ at a speed of 10 ℃/min in a reducing atmosphere, preserving heat for 2-4h, then heating to 1150-1250 ℃, preserving heat for 2-6h, and sintering to obtain a ceramic sheet;
(3) And (3) sintering the ceramic chip to infiltrate the copper electrode to prepare the ceramic capacitor.
The embodiment of the invention also provides a ceramic capacitor prepared based on the base metal pulse energy storage ceramic dielectric material.
Compared with the traditional solid phase method, the invention adopts a mode of combining the solid phase method and the sol-gel method and is assisted by the synergistic effect of ultrasonic waves, so that the granularity and the particle size distribution of main matrix powder can be effectively controlled, and simultaneously the sol-gel method assisted by ultrasonic waves can accelerate the hydrolysis process of Al precursor, shorten the synthetic reaction time, control the pore size distribution of mesoporous alumina and dope SiO 2 The mesoporous alumina nano particles are ultrasonically coated on the surface of a main matrix of a dielectric material, so that the existence of a mesoporous structure in high-temperature sintering improves that a low-melting-point phase forming a liquid phase has enough space and channels to infiltrate the surface of solid particles in the sintering process, accelerates the rearrangement of the particles of the dielectric material, reduces the sintering temperature and ensures the uniformity of the powder particles. More importantly, the base metal electrode is used for replacing the Pd/Ag inner electrode with high price, so that the requirement of reducing the production cost is met to a great extent, and a foundation is laid for researching and developing the self-controllable low-temperature and reduction-sintering-resistant pulse energy storage ceramic dielectric material.
The present invention is further illustrated by the following examples, which are not intended to limit the scope or applicability of the invention.
Example 1
A preparation method of a base metal pulse energy storage medium ceramic material comprises the following steps:
step 1, according to a formula of a base metal pulse energy storage medium ceramic material: [ a wt% (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 +bwt％(SiO 2 -Al 2 O 3 )]BaCO is processed 3 、CaCO 3 、TiO 2 And ZrO(s) 2 According to chemical formula (Ba) 0.3 Ca 0.7 )(Ti 0.3 Zr 0.7 )O 3 Is prepared according to the mole ratio of BaCO 3 And CaCO (CaCO) 3 Molar ratio 3:7, tiO 2 And ZrO(s) 2 The molar ratio is 3:7, adding raw materials in proportion, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1, adding deionized water and zirconia balls in proportion, mixing, ball milling, drying, presintering for 2 hours at 1100 ℃ to obtain (Ba) 0.3 Ca 0.7 )(Ti 0.3 Zr 0.7 )O 3 And (3) main matrix powder.
Step 2, step (Ba) 0.3 Ca 0.7 )(Ti 0.3 Zr 0.7 )O 3 Performing secondary ball milling on the main matrix powder, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1 adding deionized water and zirconia balls in proportion, ball milling, drying and sieving to obtain (Ba) 0.3 Ca 0.7 )(Ti 0.3 Zr 0.7 )O 3 Precursor powder.
Step 3, according to the main matrix (Ba 0.3 Ca 0.7 )(Ti 0.3 Zr 0.7 )O 3 Sintering aid SiO 2 -Al 2 O 3 The weight ratio is 95:5, C 9 H 21 AlO 3 Uniformly dispersing in isopropanol by means of ultrasonic waves, and performing ultrasonic dispersion for 20min to obtain a solution A.
Step 4, according to C 9 H 21 AlO 3 And PEO-PPO-PEO triblock copolymer (P123) in a weight ratio of 2.04:1, the volume ratio of the added absolute ethyl alcohol and acetic acid of P123 is 100:1, a mixed solution ofIn the solution, sonicated to dissolution followed by addition of 95wt% (Ba 0.3 Ca 0.7 )(Ti 0.3 Zr 0.7 )O 3 Precursor powder, controlling the pH value to be about 0.8, and continuing ultrasonic treatment for 30min to obtain suspension.
And 5, slowly dripping the solution A into the suspension, and continuing the ultrasonic reaction for 1h to obtain a solution B.
Step 6, according to C 9 H 21 AlO 3 And C 8 H 20 O 4 The weight ratio of Si is 10:1, C 8 H 20 O 4 Si is dissolved in absolute ethanol, then slowly added into the solution B in a dropwise manner, and the ultrasonic reaction is continued for 2 hours.
Step 7, aging the solution obtained in the step 6 for 12 hours at room temperature, drying for 10 hours at 80 ℃, and crushing and sieving through a 80-mesh screen to obtain the composition of [95wt% (Ba) 0.3 Ca 0.7 )(Ti 0.3 Zr 0.7 )O 3 +5wt％(SiO 2 -Al 2 O 3 )]Base metal pulse energy storage ceramic dielectric materials.
A method for preparing a ceramic capacitor based on the base metal pulse energy storage ceramic dielectric material comprises the following steps:
step 1, adding paraffin wax with the mass ratio of 10% into the obtained base metal pulse energy storage ceramic dielectric material for granulation, and pressing the granulated ceramic powder into a wafer green body with the diameter of 15mm and the thickness of 1.5mm under the pressure of 7 MPa.
Step 2, putting the obtained wafer green body in H 2 Heating to 500 ℃ at the speed of 10 ℃/min in the atmosphere, preserving heat for 4 hours, removing the template agent P123 and paraffin, heating to 1200 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and sintering to obtain the ceramic wafer.
And 3, sintering the sintered ceramic wafer to infiltrate the copper electrode to obtain the wafer ceramic capacitor.
The dielectric properties of the wafer-type ceramic capacitor were tested as shown in table 1:
TABLE 1 dielectric Properties parameters of wafer capacitors made from the base Metal pulse energy storage Medium ceramic Material described above
Example 2
A preparation method of a base metal pulse energy storage medium ceramic material comprises the following steps:
step 1, according to a formula of a base metal pulse energy storage medium ceramic material: [ a wt% (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 +bwt％(SiO 2 -Al 2 O 3 )]BaCO is processed 3 、CaCO 3 、TiO 2 And ZrO(s) 2 According to chemical formula (Ba) 0.4 Ca 0.6 )(Ti 0.4 Zr 0.6 )O 3 In molar ratio of BaCO 3 And CaCO (CaCO) 3 Molar ratio 4:6, tiO 2 And ZrO(s) 2 The molar ratio is 4:6, adding raw materials in proportion, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1, adding deionized water and zirconia balls in proportion, mixing, ball milling, drying, presintering for 2 hours at 1100 ℃ to obtain (Ba) 0.4 Ca 0.6 )(Ti 0.4 Zr 0.6 )O 3 And (3) main matrix powder.
Step 2, step (Ba) 0.4 Ca 0.6 )(Ti 0.4 Zr 0.6 )O 3 Performing secondary ball milling on the main matrix powder, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1 adding deionized water and zirconia balls in proportion, ball milling, drying and sieving to obtain (Ba) 0.4 Ca 0.6 )(Ti 0.4 Zr 0.6 )O 3 Precursor powder.
Step 3, according to the main matrix (Ba 0.4 Ca 0.6 )(Ti 0.4 Zr 0.6 )O 3 Sintering aid SiO 2 -Al 2 O 3 The weight ratio is 95:5, C 9 H 21 AlO 3 Uniformly dispersing in isopropanol by means of ultrasonic waves, and performing ultrasonic dispersion for 20min to obtain a solution A.
Step 4, according to C 9 H 21 AlO 3 And PEO-PPO-PEO triblock copolymer (P123) in a weight ratio of 2.04:1, the volume ratio of the added absolute ethyl alcohol and acetic acid of P123 is 100:1, followed by addition of 95 wt.% of (Ba) 0.4 Ca 0.6 )(Ti 0.4 Zr 0.6 )O 3 Precursor powder, controlling the pH value to be about 0.8, and continuing ultrasonic treatment for 30min to obtain suspension.
And 5, slowly dripping the solution A into the suspension, and continuing the ultrasonic reaction for 1h to obtain a solution B.
Step 6, according to C 9 H 21 AlO 3 And C 8 H 20 O 4 Si weight ratio is 10:1, C 8 H 20 O 4 Si is dissolved in absolute ethanol, then slowly added into the solution B in a dropwise manner, and the ultrasonic reaction is continued for 2 hours.
Step 7, aging the solution obtained in the step 6 for 12 hours at room temperature, drying for 10 hours at 80 ℃, and crushing and sieving through a 80-mesh screen to obtain the composition of [95wt% (Ba) 0.4 Ca 0.6 )(Ti 0.4 Zr 0.6 )O 3 +5wt％(SiO 2 -Al 2 O 3 )]Base metal pulse energy storage ceramic dielectric materials.
A method for preparing a ceramic capacitor based on the base metal pulse energy storage ceramic dielectric material comprises the following steps:
step 1, adding paraffin wax with the mass ratio of 10% into the obtained base metal pulse energy storage ceramic dielectric material for granulation, and pressing the granulated ceramic powder into a wafer green body with the diameter of 15mm and the thickness of 1.5mm under the pressure of 7 MPa.
Step 2, putting the obtained wafer green body in H 2 Heating to 500 ℃ at the speed of 10 ℃/min in the atmosphere, preserving heat for 4 hours, removing the template agent P123 and paraffin, heating to 1200 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and sintering to obtain the ceramic wafer.
And 3, sintering the sintered ceramic wafer to infiltrate the copper electrode to obtain the wafer ceramic capacitor.
The dielectric properties of the wafer ceramic capacitors were tested as shown in table 2:
TABLE 2 dielectric Properties parameters of wafer capacitors made from the base Metal pulse energy storage Medium ceramic Material described above
Example 3
A preparation method of a base metal pulse energy storage medium ceramic material comprises the following steps:
step 1, according to a formula of a base metal pulse energy storage medium ceramic material: [ a wt% (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 +bwt％(SiO 2 -Al 2 O 3 )]BaCO is processed 3 、CaCO 3 、TiO 2 And ZrO(s) 2 According to chemical formula (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 In molar ratio of BaCO 3 And CaCO (CaCO) 3 Molar ratio 6:4, tiO 2 And ZrO(s) 2 The molar ratio is 6:4, adding raw materials in proportion, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1, adding deionized water and zirconia balls in proportion, mixing, ball milling, drying, presintering for 2 hours at 1100 ℃ to obtain (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 And (3) main matrix powder.
Step 2, step (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Performing secondary ball milling on the main matrix powder, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1 adding deionized water and zirconia balls in proportion, ball milling, drying and sieving to obtain (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Precursor powder.
Step 3, according to the main matrix (Ba 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Sintering aid SiO 2 -Al 2 O 3 The weight ratio is 95:5, C 9 H 21 AlO 3 Uniformly dispersed in isopropyl by means of ultrasonic waveAnd (3) performing ultrasonic dispersion in alcohol for 20min to obtain a solution A.
Step 4, according to C 9 H 21 AlO 3 And PEO-PPO-PEO triblock copolymer (P123) in a weight ratio of 2.04:1, the ratio of P123 to absolute ethanol to acetic acid was 100:1, followed by addition of 95 wt.% of (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Precursor powder, controlling the pH value to be about 0.8, and continuing ultrasonic treatment for 30min to obtain suspension.
And 5, slowly dripping the solution A into the suspension, and continuing the ultrasonic reaction for 1h to obtain a solution B.
Step 6, according to C 9 H 21 AlO 3 And C 8 H 20 O 4 Si weight ratio is 10:1, C 8 H 20 O 4 Si is dissolved in absolute ethanol, then slowly added into the solution B in a dropwise manner, and the ultrasonic reaction is continued for 2 hours.
Step 7, aging the solution obtained in the step 6 for 12 hours at room temperature, drying for 10 hours at 80 ℃, and crushing and sieving through a 80-mesh screen to obtain the composition of [95wt% (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 +5wt％(SiO 2 -Al 2 O 3 )]Base metal pulse energy storage ceramic dielectric materials.
A method for preparing a ceramic capacitor based on the base metal pulse energy storage ceramic dielectric material comprises the following steps:
step 1, adding paraffin wax with the mass ratio of 10% into the obtained base metal pulse energy storage ceramic dielectric material for granulation, and pressing the granulated ceramic powder into a wafer green body with the diameter of 15mm and the thickness of 1.5mm under the pressure of 7 MPa.
Step 2, putting the obtained wafer green body in H 2 Heating to 500 ℃ at the speed of 10 ℃/min in the atmosphere, preserving heat for 4 hours, removing the template agent P123 and paraffin, heating to 1200 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and sintering to obtain the ceramic wafer.
And 3, sintering the sintered ceramic wafer to infiltrate the copper electrode to obtain the wafer ceramic capacitor.
The dielectric properties of the wafer-type ceramic capacitor were tested as shown in table 3:
TABLE 3 dielectric Properties parameters of wafer capacitors made from the base Metal pulse energy storage Medium ceramic Material described above
Example 4
A preparation method of a base metal pulse energy storage medium ceramic material comprises the following steps:
step 1, according to a formula of a base metal pulse energy storage medium ceramic material: [ a wt% (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 +bwt％(SiO 2 -Al 2 O 3 )]BaCO is processed 3 、CaCO 3 、TiO 2 And ZrO(s) 2 According to chemical formula (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 In molar ratio of BaCO 3 And CaCO (CaCO) 3 Molar ratio 6:4, tiO 2 And ZrO(s) 2 The molar ratio is 6:4, adding raw materials in proportion, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1, adding deionized water and zirconia balls in proportion, mixing, ball milling, drying, presintering for 2 hours at 1100 ℃ to obtain (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 And (3) main matrix powder.
Step 2, step (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Performing secondary ball milling on the main matrix powder, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1 adding deionized water and zirconia balls in proportion, ball milling, drying and sieving to obtain (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Precursor powder.
Step 3, according to the main matrix (Ba 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Sintering aid SiO 2 -Al 2 O 3 The weight ratio is 93: ratio of 7, C 9 H 21 AlO 3 Uniformly dispersing in isopropanol by means of ultrasonic waves, and performing ultrasonic dispersion for 20min to obtain a solution A.
Step 4, according to C 9 H 21 AlO 3 And PEO-PPO-PEO triblock copolymer (P123) in a weight ratio of 2.04:1, the volume ratio of the added absolute ethyl alcohol and acetic acid of P123 is 100:1, followed by adding 93wt% of (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Precursor powder, controlling the pH value to be about 0.8, and continuing ultrasonic treatment for 30min to obtain suspension.
And 5, slowly dripping the solution A into the suspension, and continuing the ultrasonic reaction for 1h to obtain a solution B.
Step 6, according to C 9 H 21 AlO 3 And C 8 H 20 O 4 Si weight ratio is 10:1, C 8 H 20 O 4 Si is dissolved in absolute ethanol, then slowly added into the solution B in a dropwise manner, and the ultrasonic reaction is continued for 2 hours.
Step 7, aging the solution obtained in the step 6 for 12 hours at room temperature, drying for 10 hours at 80 ℃, and crushing and sieving through a 80-mesh screen to obtain the composition of [93wt% (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 +7wt％(SiO 2 -Al 2 O 3 )]Base metal pulse energy storage ceramic dielectric materials.
A method for preparing a ceramic capacitor based on the base metal pulse energy storage ceramic dielectric material comprises the following steps:
step 1, adding paraffin wax with the mass ratio of 10% into the obtained base metal pulse energy storage ceramic dielectric material for granulation, and pressing the granulated ceramic powder into a wafer green body with the diameter of 15mm and the thickness of 1.5mm under the pressure of 7 MPa.
Step 2, putting the obtained wafer green body in H 2 Heating to 500 ℃ at the speed of 10 ℃/min in the atmosphere, preserving heat for 4 hours, removing the template agent P123 and paraffin, heating to 1200 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and sintering to obtain base metal pulseAn energy storage dielectric ceramic material.
And 3, sintering the sintered base metal pulse energy storage medium ceramic material to infiltrate the copper electrode to prepare the wafer ceramic capacitor.
The dielectric properties of the wafer-type ceramic capacitor were tested as shown in table 4:
TABLE 4 dielectric Properties parameters of wafer capacitors made from the base Metal pulse energy storage Medium ceramic Material described above
Comparative example 1
A preparation method of a base metal pulse energy storage medium ceramic material comprises the following steps:
step 1, according to a formula of a base metal pulse energy storage medium ceramic material: [ a wt% (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 +bwt％(SiO 2 -Al 2 O 3 )]BaCO is processed 3 、CaCO 3 、TiO 2 And ZrO(s) 2 According to chemical formula (Ba) 0.8 Ca 0.2 )(Ti 0.8 Zr 0.2 )O 3 In molar ratio of BaCO 3 And CaCO (CaCO) 3 Molar ratio 8:2, tiO 2 And ZrO(s) 2 The molar ratio is 8:2, adding raw materials in proportion, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1, adding deionized water and zirconia balls in proportion, mixing, ball milling, drying, presintering for 2 hours at 1100 ℃ to obtain (Ba) 0.8 Ca 0.2 )(Ti 0.8 Zr 0.2 )O 3 And (3) main matrix powder.
Step 2, step (Ba) 0.8 Ca 0.2 )(Ti 0.8 Zr 0.2 )O 3 Performing secondary ball milling on the main matrix powder, and deionized water according to the weight ratio: material = 2:1,2.0mm oxidationZirconium ball: material = 5:1 adding deionized water and zirconia balls in proportion, ball milling, drying and sieving to obtain (Ba) 0.8 Ca 0.2 )(Ti 0.8 Zr 0.2 )O 3 Precursor powder.
Step 3, according to the main matrix (Ba 0.8 Ca 0.2 )(Ti 0.8 Zr 0.2 )O 3 Sintering aid SiO 2 -Al 2 O 3 The weight ratio is 93: ratio of 7, C 9 H 21 AlO 3 Uniformly dispersing in isopropanol by means of ultrasonic waves, and performing ultrasonic dispersion for 20min to obtain a solution A.
Step 4, according to C 9 H 21 AlO 3 And PEO-PPO-PEO triblock copolymer (P123) in a weight ratio of 2.04:1, the volume ratio of the added absolute ethyl alcohol and acetic acid of P123 is 100:1, followed by adding 93wt% of (Ba) 0.8 Ca 0.2 )(Ti 0.8 Zr 0.2 )O 3 Precursor powder, controlling the pH value to be about 0.8, and continuing ultrasonic treatment for 30min to obtain suspension.
And 5, slowly dripping the solution A into the suspension, and continuing the ultrasonic reaction for 1h to obtain a solution B.
Step 6, according to C 9 H 21 AlO 3 And C 8 H 20 O 4 Si weight ratio is 10:1, C 8 H 20 O 4 Si is dissolved in absolute ethanol, then slowly added into the solution B in a dropwise manner, and the ultrasonic reaction is continued for 2 hours.
Step 7, aging the solution obtained in the step 6 for 12 hours at room temperature, drying for 10 hours at 80 ℃, and crushing and sieving through a 80-mesh screen to obtain the composition of [93wt% (Ba) 0.8 Ca 0.2 )(Ti 0.8 Zr 0.2 )O 3 +7wt％(SiO 2 -Al 2 O 3 )]Base metal pulse energy storage ceramic dielectric materials.
A method for preparing a ceramic capacitor based on the base metal pulse energy storage ceramic dielectric material comprises the following steps:
step 1, adding paraffin wax with the mass ratio of 10% into the obtained base metal pulse energy storage ceramic dielectric material for granulation, and pressing the granulated ceramic powder into a wafer green body with the diameter of 15mm and the thickness of 1.5mm under the pressure of 7 MPa.
Step 2, putting the obtained wafer green body in H 2 Heating to 500 ℃ at the speed of 10 ℃/min in the atmosphere, preserving heat for 4 hours, removing the template agent P123 and paraffin, heating to 1200 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and sintering to obtain the base metal pulse energy storage medium ceramic material.
And 3, sintering the sintered base metal pulse energy storage medium ceramic material to infiltrate the copper electrode to prepare the wafer ceramic capacitor.
The dielectric properties of the wafer-type ceramic capacitor were tested as shown in table 4:
TABLE 5 dielectric Properties parameters of wafer capacitors made from the base Metal pulse energy storage Medium ceramic Material described above
Comparative example 2
A preparation method of a base metal pulse energy storage medium ceramic material comprises the following steps:
step 1, according to a formula of a base metal pulse energy storage medium ceramic material: [ a wt% (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 +bwt％(SiO 2 -Al 2 O 3 )]BaCO is processed 3 、CaCO 3 、TiO 2 And ZrO(s) 2 According to chemical formula (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 In molar ratio of BaCO 3 And CaCO (CaCO) 3 Molar ratio 6:4, tiO 2 And ZrO(s) 2 The molar ratio is 6:4, adding raw materials in proportion, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1, adding deionized water and zirconia balls in proportion, mixing, ball milling, drying, presintering for 2 hours at 1100 ℃ to obtain (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 And (3) main matrix powder.
Step 2, step (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Performing secondary ball milling on the main matrix powder, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1 adding deionized water and zirconia balls in proportion, ball milling, drying and sieving to obtain (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Precursor powder.
Step 3, according to the main matrix (Ba 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Sintering aid SiO 2 -Al 2 O 3 The weight ratio is 83:17, C 9 H 21 AlO 3 Uniformly dispersing in isopropanol by means of ultrasonic waves, and performing ultrasonic dispersion for 20min to obtain a solution A.
Step 4, according to C 9 H 21 AlO 3 And PEO-PPO-PEO triblock copolymer (P123) in a weight ratio of 2.04:1, the volume ratio of the added absolute ethyl alcohol and acetic acid of P123 is 100:1, followed by adding 93wt% of (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Precursor powder, controlling the pH value to be about 0.8, and continuing ultrasonic treatment for 30min to obtain suspension.
And 5, slowly dripping the solution A into the suspension, and continuing the ultrasonic reaction for 1h to obtain a solution B.
Step 6, according to C 9 H 21 AlO 3 And C 8 H 20 O 4 Si weight ratio is 10:1, C 8 H 20 O 4 Si is dissolved in absolute ethanol, then slowly added into the solution B in a dropwise manner, and the ultrasonic reaction is continued for 2 hours.
Step 7, aging the solution obtained in the step 6 for 12 hours at room temperature, drying for 10 hours at 80 ℃, and crushing and sieving through a 80-mesh screen to obtain a composition of [83wt% (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 +17wt％(SiO 2 -Al 2 O 3 )]Base metal pulse energy storage ceramic dielectric materials.
A method for preparing a ceramic capacitor based on the base metal pulse energy storage ceramic dielectric material comprises the following steps:
step 1, adding paraffin wax with the mass ratio of 10% into the obtained base metal pulse energy storage ceramic dielectric material for granulation, and pressing the granulated ceramic powder into a wafer green body with the diameter of 15mm and the thickness of 1.5mm under the pressure of 7 MPa.
Step 2, putting the obtained wafer green body in H 2 Heating to 500 ℃ at the speed of 10 ℃/min in the atmosphere, preserving heat for 4 hours, removing the template agent P123 and paraffin, heating to 1200 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and sintering to obtain the base metal pulse energy storage medium ceramic material.
And 3, sintering the sintered base metal pulse energy storage medium ceramic material to infiltrate the copper electrode to prepare the wafer ceramic capacitor.
The dielectric properties of the wafer-type ceramic capacitor were tested as shown in table 4:
TABLE 6 dielectric Properties parameters of wafer capacitors made from the base Metal pulse energy storage Medium ceramic Material described above
Comparative example 3
A preparation method of a base metal pulse energy storage medium ceramic material comprises the following steps:
step 1, according to a formula of a base metal pulse energy storage medium ceramic material: [ a wt% (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 +bwt％(B 2 O 3 -Al 2 O 3 )]BaCO is processed 3 、CaCO 3 、TiO 2 And ZrO(s) 2 According to chemical formula (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 In molar ratio of BaCO 3 And CaCO (CaCO) 3 Molar ratio 6:4, tiO 2 And ZrO(s) 2 The molar ratio is 6:4, adding raw materials in proportion, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1 ratio of deionized water and oxygenZirconium ball is mixed, ball milled, dried and presintered for 2 hours at 1100 ℃ to obtain (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 And (3) main matrix powder.
Step 2, step (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Performing secondary ball milling on the main matrix powder, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1 adding deionized water and zirconia balls in proportion, ball milling, drying and sieving to obtain (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Precursor powder.
Step 3, according to the main matrix (Ba 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 And sintering aid B 2 O 3 -Al 2 O 3 The weight ratio is 93: ratio of 7, C 9 H 21 AlO 3 Uniformly dispersing in isopropanol by means of ultrasonic waves, and performing ultrasonic dispersion for 20min to obtain a solution A.
Step 4, according to C 9 H 21 AlO 3 And PEO-PPO-PEO triblock copolymer (P123) in a weight ratio of 2.04:1, the volume ratio of the added absolute ethyl alcohol and acetic acid of P123 is 100:1, followed by adding 93wt% of (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Precursor powder, controlling the pH value to be about 0.8, and continuing ultrasonic treatment for 30min to obtain suspension.
And 5, slowly dripping the solution A into the suspension, and continuing the ultrasonic reaction for 1h to obtain a solution B.
Step 6, according to C 9 H 21 AlO 3 And H 3 BO 3 The weight ratio is 10:1, H 3 BO 3 Dispersing the solution in absolute ethyl alcohol by ultrasonic, then slowly dripping the solution into the solution B, and continuing ultrasonic reaction for 2 hours.
Step 7, aging the solution obtained in the step 6 for 12 hours at room temperature, drying for 10 hours at 80 ℃, and crushing and sieving through a 80-mesh screen to obtain a composition of [83wt% (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 +17wt％(B 2 O 3 -Al 2 O 3 )]Base metal pulse energy storage ceramic dielectric materials.
A method for preparing a ceramic capacitor based on the base metal pulse energy storage ceramic dielectric material comprises the following steps:
step 1, adding paraffin wax with the mass ratio of 10% into the obtained base metal pulse energy storage ceramic dielectric material for granulation, and pressing the granulated ceramic powder into a wafer green body with the diameter of 15mm and the thickness of 1.5mm under the pressure of 7 MPa.
Step 2, putting the obtained wafer green body in H 2 Heating to 500 ℃ at the speed of 10 ℃/min in the atmosphere, preserving heat for 4 hours, removing the template agent P123 and paraffin, heating to 1200 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and sintering to obtain the base metal pulse energy storage medium ceramic material.
And 3, sintering the sintered base metal pulse energy storage medium ceramic material to infiltrate the copper electrode to prepare the wafer ceramic capacitor.
The dielectric properties of the wafer-type ceramic capacitor were tested as shown in table 4:
TABLE 7 dielectric Properties parameters of wafer capacitors made from the base Metal pulse energy storage Medium ceramic Material described above
Comparative example 4
A preparation method of a base metal pulse energy storage medium ceramic material comprises the following steps:
step 1, according to a formula of a base metal pulse energy storage medium ceramic material: [ a wt% (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 +bwt％(SiO 2 -Al 2 O 3 )]BaCO is processed 3 、CaCO 3 、TiO 2 And ZrO(s) 2 According to chemical formula (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 In molar ratio of BaCO 3 And CaCO (CaCO) 3 Molar ratio 6:4，TiO 2 And ZrO(s) 2 The molar ratio is 6:4, adding raw materials in proportion, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1, adding deionized water and zirconia balls in proportion, mixing, ball milling, drying, presintering for 2 hours at 1100 ℃ to obtain (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 And (3) main matrix powder.
Step 2, step (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Performing secondary ball milling on the main matrix powder, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1 adding deionized water and zirconia balls in proportion, ball milling, drying and sieving to obtain (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Precursor powder.
Step 3, according to the main matrix (Ba 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Sintering aid SiO 2 -Al 2 O 3 The weight ratio is 93:7 ratio, C was stirred by means of a magnetic stirrer 9 H 21 AlO 3 Uniformly dispersing in isopropanol, and stirring for 20min to obtain a solution A.
Step 4, according to C 9 H 21 AlO 3 And PEO-PPO-PEO triblock copolymer (P123) in a weight ratio of 2.04:1, the volume ratio of the added absolute ethyl alcohol and acetic acid of P123 is 100:1, followed by adding 93wt% of (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Precursor powder, controlling the pH value to be about 0.8, and continuously stirring for 30min to obtain suspension.
And 5, slowly dripping the solution A into the suspension, and continuously stirring and reacting for 1h to obtain the solution B.
Step 6, according to C 9 H 21 AlO 3 And C 8 H 20 O 4 Si weight ratio is 10:1, C 8 H 20 O 4 Si was dissolved in absolute ethanol, then slowly added dropwise to solution B, and the reaction was continued with stirring for 2h.
Step (a)7, aging the solution obtained in the step 6 for 12 hours at room temperature, drying for 10 hours at 80 ℃, and crushing and sieving through a 80-mesh screen to obtain the composition of [93wt% (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 +7wt％(SiO 2 -Al 2 O 3 )]Base metal pulse energy storage ceramic dielectric materials.
A method for preparing a ceramic capacitor based on the base metal pulse energy storage ceramic dielectric material comprises the following steps:
step 1, adding paraffin wax with the mass ratio of 10% into the obtained base metal pulse energy storage ceramic dielectric material for granulation, and pressing the granulated ceramic powder into a wafer green body with the diameter of 15mm and the thickness of 1.5mm under the pressure of 7 MPa.
Step 2, putting the obtained wafer green body in H 2 Heating to 500 ℃ at the speed of 10 ℃/min in the atmosphere, preserving heat for 4 hours, removing the template agent P123 and paraffin, heating to 1200 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and sintering to obtain the base metal pulse energy storage medium ceramic material.
And 3, sintering the sintered base metal pulse energy storage medium ceramic material to infiltrate the copper electrode to prepare the wafer ceramic capacitor.
The dielectric properties of the wafer-type ceramic capacitor were tested as shown in table 4:
TABLE 8 dielectric Properties parameters of wafer capacitors made from the base Metal pulse energy storage Medium ceramic Material described above
Comparative example 5
A preparation method of a base metal pulse energy storage medium ceramic material comprises the following steps:
step 1, according to a formula of a base metal pulse energy storage medium ceramic material: [ a wt% (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 +bwt％(SiO 2 -Al 2 O 3 )]BaCO is processed 3 、CaCO 3 、TiO 2 And ZrO(s) 2 According to chemical formula (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 In molar ratio of BaCO 3 And CaCO (CaCO) 3 Molar ratio 6:4, tiO 2 And ZrO(s) 2 The molar ratio is 6:4, adding raw materials in proportion, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1, adding deionized water and zirconia balls in proportion, mixing, ball milling, drying, presintering for 2 hours at 1100 ℃ to obtain (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 And (3) main matrix powder.
Step 2, according to the main matrix (Ba 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Sintering aid SiO 2 -Al 2 O 3 The weight ratio is 93: ratio of 7, C 9 H 21 AlO 3 And C 8 H 20 O 4 Si weight ratio is 10:1, C 9 H 21 AlO 3 And C 8 H 20 O 4 Si and host matrix (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 Evenly mixing, and deionized water according to the weight ratio: material = 2:1,2.0mm zirconia balls: material = 5:1, adding deionized water and zirconia balls in proportion, mixing and ball milling;
step 3, drying the mixed solution obtained in the step 2, and crushing and sieving the dried mixed solution through a 80-mesh screen to obtain a composition of [93wt% (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 +7wt％(SiO 2 -Al 2 O 3 )]Base metal pulse energy storage ceramic dielectric materials.
A method for preparing a ceramic capacitor based on the base metal pulse energy storage ceramic dielectric material comprises the following steps:
step 1, adding paraffin wax with the mass ratio of 10% into the obtained base metal pulse energy storage ceramic dielectric material for granulation, and pressing the granulated ceramic powder into a wafer green body with the diameter of 15mm and the thickness of 1.5mm under the pressure of 7 MPa.
Step 2, putting the obtained wafer green body in H 2 Heating to 500 ℃ at the speed of 10 ℃/min in the atmosphere, preserving heat for 4 hours, removing the template agent P123 and paraffin, heating to 1200 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and sintering to obtain the base metal pulse energy storage medium ceramic material.
And 3, sintering the sintered base metal pulse energy storage medium ceramic material to infiltrate the copper electrode to prepare the wafer ceramic capacitor.
The dielectric properties of the wafer-type ceramic capacitor were tested as shown in table 4:
TABLE 9 dielectric Properties parameters of wafer capacitors made from the base Metal pulse energy storage Medium ceramic Material described above
As shown in FIG. 1, the ceramic capacitors prepared in examples 1-4 were tested for the rate of change of capacitance and temperature, and the ceramic dielectric powders prepared in examples 1-4 were found to have a capacitance and temperature change in the range (-2200 to-1000) ppm/K, and were stable in the change curves. In combination with the basic electrical parameters shown in tables 1-4, it can be seen that BaCO 3 And CaCO (CaCO) 3 Molar ratio 6:4, tiO 2 And ZrO(s) 2 The molar ratio is 6:4, and the ratio of the main matrix to the sintering aid is 93:7, and by means of an ultrasound-assisted sol-gel process [93 wt.% (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 +7wt％(SiO 2 -Al 2 O 3 )]The base metal pulse energy storage ceramic dielectric material has moderate dielectric constant and low dielectric loss, and has excellent resistivity and compressive strength at normal temperature and high temperature.
By observing the SEM microscopic morphology of the base metal pulse energy storage medium ceramic materials prepared in example 3 and example 4, as shown in fig. 2, wherein fig. 2 (a) is a SEM result graph of the base metal pulse energy storage medium ceramic material prepared in example 3, and fig. 2 (b) is a SEM result graph of the base metal pulse energy storage medium ceramic material prepared in example 4. As can be seen from SEM result, the main matrix has uniform particle size distribution and main particle sizeDistributed between 300-500nm, and doped SiO is attached to the surface of the main matrix 2 Mesoporous alumina nanoparticles of (a).
As is clear from comparison of example 4 with comparative examples 1 and 2, increasing the amounts of Ba and Ti increases the dielectric constant, but the loss is high, the resistivity is lowered and the withstand voltage is attenuated to some extent, which is probably due to the higher content of Ba and Ti, insufficient sintering temperature, and deterioration of performance; increasing the proportion of sintering aid also leads to deterioration of properties, possibly due to the presence of excess sintering aid, resulting in non-uniform particle size distribution after sintering, partial SiO 2 -Al 2 O 3 There is an agglomeration phenomenon.
As can be seen from the comparison of example 4 with comparative example 3, the use of B 2 O 3 -Al 2 O 3 Substitute for sintering aid SiO 2 -Al 2 O 3 The dielectric loss of the porcelain powder is greatly increased, the resistivity and the dielectric withstand voltage are reduced, therefore, B is adopted 2 O 3 -Al 2 O 3 Is sintering aid and (Ba) 0.6 Ca 0.4 )(Ti 0.6 Zr 0.4 )O 3 The porcelain powder which is the main matrix is not fit.
As can be seen from comparison of example 4 with comparative examples 4 and 5, the introduction of ultrasonic waves can promote the aggregation of hydrophilic polyethylene oxide (PEO) ends in P123 in the solution to the direction of the solution, and hydrophobic polypropylene oxide (PPO) ends are close to each other, so that the acoustic cavitation effect of the ultrasonic waves greatly accelerates the self-assembly to form aluminum species coated P123 micelles. The ultrasonic-assisted sol-gel method is beneficial to improving the uniformity of the sintering aid to be coated on the surface of the main matrix, improving the sintering uniformity of the ceramic powder and showing more excellent performance.
While the application has been described with reference to specific embodiments, the scope of the application is not limited thereto, and any changes or substitutions can be easily made by those skilled in the art within the scope of the application disclosed herein, and are intended to be covered by the scope of the application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims (7)

1. Base metal pulse energy storage ceramic mediumThe material is characterized by comprising the following components in percentage by weight: [ awt% (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 +b wt％(SiO 2 -Al 2 O 3 )]Wherein, (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 SiO as a main matrix 2 -Al 2 O 3 As sintering auxiliary agents, x is more than or equal to 0.4 and less than or equal to 0.7,0.4, y is more than or equal to 0.7, a is more than or equal to 85 and less than or equal to 98, b is more than or equal to 2 and less than or equal to 15, and a and b are respectively the mass percentages of the main matrix and the sintering auxiliary agents, and the sintering auxiliary agents are prepared by adopting the following method:
Step 1, baCO 3 、CaCO 3 、TiO 2 And ZrO(s) 2 Preparing raw materials, ball milling, drying, crushing and presintering by using deionized water as a dispersion medium to obtain (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 Powder;
step 2, step (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 Ball milling, drying and sieving the powder to obtain
(Ba 1-x Ca x )(Ti 1-y Zr y )O 3 Precursor powder;
step 3, according to SiO 2 -Al 2 O 3 Is prepared from C 9 H 21 AlO 3 Ultrasonic dispersing in isopropanol, wherein the power of ultrasonic dispersing is 300-600W, the temperature of ultrasonic dispersing is 25-35 ℃, and the time of ultrasonic dispersing is 10-20min;
step 4, adding the PEO-PPO-PEO triblock copolymer into a mixed solution of absolute ethyl alcohol and acetic acid, and performing ultrasonic dispersion until the PEO-PPO-PEO triblock copolymer is dissolved, wherein the volume ratio of the absolute ethyl alcohol to the acetic acid is 100:1, adding the (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 Precursor powder, controlling the pH value to be about 0.5-1.5, continuing ultrasonic treatment to obtain suspension, and performing ultrasonic dispersion for 10-30min;
step 5, slowly dripping the solution obtained in the step 3 into the suspension, and uniformly dispersing and mixing by ultrasonic to obtain a mixed solution, wherein the ultrasonic dispersing time is 0.5-2 h;
step 6, C 8 H 20 O 4 Si is dissolved in absolute ethyl alcohol, then is slowly dripped into the mixed solution, and continues to carry out ultrasonic dispersion reaction, wherein the ultrasonic dispersion time is 0.5h-2h;
and 7, aging, drying, crushing and sieving the solution obtained in the step 6 at room temperature to obtain the base metal pulse energy storage ceramic dielectric material.
2. A method of preparing a base metal pulse energy storage ceramic dielectric material according to claim 1, comprising the steps of:
step 1, baCO 3 、CaCO 3 、TiO 2 And ZrO(s) 2 Preparing raw materials, ball milling, drying, crushing and presintering by using deionized water as a dispersion medium to obtain (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 Powder;
step 2, step (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 Ball milling, drying and sieving the powder to obtain
(Ba 1-x Ca x )(Ti 1-y Zr y )O 3 Precursor powder;
step 3, according to SiO 2 -Al 2 O 3 Is prepared from C 9 H 21 AlO 3 Ultrasonic dispersing in isopropanol, wherein the power of ultrasonic dispersing is 300-600W, the temperature of ultrasonic dispersing is 25-35 ℃, and the time of ultrasonic dispersing is 10-20min;
step 4, adding the PEO-PPO-PEO triblock copolymer into a mixed solution of absolute ethyl alcohol and acetic acid, and performing ultrasonic dispersion until the PEO-PPO-PEO triblock copolymer is dissolved, wherein the volume ratio of the absolute ethyl alcohol to the acetic acid is 100:1, adding the (Ba) 1-x Ca x )(Ti 1-y Zr y )O 3 Precursor powder, controlling the pH value to be about 0.5-1.5, continuing ultrasonic treatment to obtain suspension, and performing ultrasonic dispersion for 10-30min;
step 5, slowly dripping the solution obtained in the step 3 into the suspension, and uniformly dispersing and mixing by ultrasonic to obtain a mixed solution, wherein the ultrasonic dispersing time is 0.5-2 h;
step 6, C 8 H 20 O 4 Si is dissolved in absolute ethyl alcohol, then is slowly dripped into the mixed solution, and continues to carry out ultrasonic dispersion reaction, wherein the ultrasonic dispersion time is 0.5h-2h;
And 7, aging, drying, crushing and sieving the solution obtained in the step 6 at room temperature to obtain the base metal pulse energy storage ceramic dielectric material.
3. The method for preparing the base metal pulse energy storage ceramic dielectric material according to claim 2, wherein the weight ratio of deionized water to materials in the ball milling process of step 1 and step 2 is 2:1, the ball milling medium adopted is zirconia balls, and the weight ratio of the ball milling medium to the materials is 5:1, the rotating speed is 400-600rpm/min, and the ball milling time is 2-6h.
4. The method for preparing the base metal pulse energy storage ceramic dielectric material according to claim 2, wherein the temperature of drying in the step 1 and the step 2 is 120-150 ℃ and the drying time is 4-12h; the presintering temperature in the step 1 is 900-1100 ℃, and the heat preservation time is 2-4h.
5. The method for preparing a base metal pulse energy storage ceramic dielectric material according to claim 2, wherein the aging temperature in the step 7 is 25 ℃ and the aging time is 6-12h; the drying temperature is 60-80 ℃, and the drying time is 6-12h.
6. A method of making a ceramic capacitor based on the base metal pulsed energy storage ceramic dielectric material of claim 1, comprising the steps of:
Step 1, sieving the base metal pulse energy storage ceramic dielectric material, adding 8-10wt% of paraffin wax for granulation, and pressing into a green body under 5-8 Mpa;
step 2, the green body is processed in H 2 Heating to 500 ℃ at a speed of 10 ℃/min in a reducing atmosphere, preserving heat for 2-4h, and then heating to 1150-12Preserving heat for 2-6h at 50 ℃ and sintering into ceramic sheets;
and 3, sintering the ceramic sheet to infiltrate the copper electrode to prepare the ceramic capacitor.
7. A ceramic capacitor prepared based on the base metal pulse energy storage ceramic dielectric material of claim 1.
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