CN113896525A - Medium material with stable medium and low firing temperature and preparation method thereof - Google Patents

Medium material with stable medium and low firing temperature and preparation method thereof Download PDF

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CN113896525A
CN113896525A CN202111320955.1A CN202111320955A CN113896525A CN 113896525 A CN113896525 A CN 113896525A CN 202111320955 A CN202111320955 A CN 202111320955A CN 113896525 A CN113896525 A CN 113896525A
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黄雪琛
龙慧娟
陈亚西
王珊珊
曾默涵
杨怡晴
闻欣欣
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Abstract

The invention discloses a medium material with stable medium and low firing temperature and a preparation method thereof3、Nb(OH)5、Cu(NO3)2、Ti(OC4O9)4、Bi(NO3)3·5H2O、NaNO3·H2O、Zn(NO3)2·6H2O、Ba(NO3)2Tributyl borate and tetraethyl silicate. The dielectric ceramic prepared by the invention has the advantages of low sintering temperature, excellent temperature stability, cheap formula raw materials, simple preparation process, sintering temperature of 900 ℃, material room temperature dielectric constant of 896, room temperature dielectric loss of 0.019, temperature change rate of not more than +/-15% in the temperature range of-55-200 ℃, and room temperature resistivity of 6.5 multiplied by 1011Multilayer ceramic capacitor dielectric satisfying X9R characteristicsThe requirements of ceramic.

Description

Medium material with stable medium and low firing temperature and preparation method thereof
Technical Field
The invention relates to the field of ceramic capacitor dielectric materials, in particular to a medium-low-sintering-temperature stable type dielectric material and a preparation method thereof.
Background
A multilayer ceramic capacitor MLCC (multi-1 oxygen ceramic capacitor) is one of the most used and developed chip passive components in the world. MLCC has the advantages of small size, low internal inductance, high insulation resistance, low leakage current, low dielectric loss, low cost, etc., and is widely used in oscillation, coupling, filtering and bypass circuits in various electronic machines. In recent years, MLCC is used for electronic devices such as automobile engines, such as engine electronic control units, crank angle sensors, and anti-lock brake systems, which operate in severe environments, especially at operating temperatures of 130 ℃ or higher in summer, and this requires MLCC dielectric materials to have excellent capacitance-temperature stability characteristics at wide operating temperatures in order to ensure stable operation of automobile engine control, drive control, and brake control systems; the electronics used to search for oil and gas reserves are subjected to temperatures in excess of 200 c. Obviously, X7R (satisfying Δ C/C in the temperature range of-55 to 125 DEG)25℃Less than or equal to 15 percent) and X8R (meeting the delta C/C within the temperature range of-55 to 150 DEG)25℃Less than or equal to 15 percent) of the dielectric materials can not meet the actual requirements under severe environment, and the upper limits of the use temperatures of the dielectric materials are 125 ℃ and 150 ℃, so that higher temperature stability X9R (meeting the delta C/C within the temperature range of-55-200 ℃) is developed25℃15%) of the dielectric material of the capacitor, and has very important practical application dielectric.
A multilayer ceramic capacitor has a co-fired monolithic structure in which a dielectric material and internal electrodes (silver, silver palladium, etc.) are stacked in a staggered manner, and thus the melting point of the internal electrodes is required to be higher than the sintering temperature of the dielectric material. The price and the characteristics of the internal electrode material sintered in the air atmosphere are shown in Table 1, the melting point of the sintered metal in the air is in direct proportion to the price of the metal, and the melting points of palladium and platinum are notThe sintering temperature of the dielectric material is increased when the material is used as an electrode, but the price is very high compared with other metals, which is very unfavorable for the production of Ag and Ag70-Pd30The production cost can be greatly reduced, and the sintering temperature of the dielectric material needs to be reduced. Therefore, the research on the X9R dielectric ceramic with low firing width working temperature has very important significance.
TABLE 1 price and characteristics of air atmosphere sintered internal electrode materials
Figure BDA0003345137220000011
Disclosure of Invention
The technical problems to be solved by the invention are as follows: how to prepare the dielectric material of the ceramic capacitor at medium and low sintering temperature.
To solve the above problems, the present invention provides the following technical solutions
A medium material with medium-low combustion temperature stability contains BaTiO as main component3The main component and Nb (OH)5、Cu(NO3)2、Ti(OC4O9)4、Bi(NO3)3·5H2O、NaNO3·H2O、Zn(NO3)2·6H2O、Ba(NO3)2The boric acid tributyl ester and the tetraethyl silicate are prepared by the steps of dissolving and sintering.
Preferably, said Nb (OH)5The dosage of the Cu (NO) accounts for 0.2 to 2 percent of the mass of the main component3)2The dosage of the Bi (NO) accounts for 0 to 15 percent of the mass of the main component3)2·5H2The dosage of O is 5 to 60 percent of the mass of the main component, and Ti (OC)4O9)4The dosage of the composition is 5 to 20 percent of the mass of the main component, the dosage of the tetraethyl silicate is 0 to 0.1 percent of the mass of the main component, and the NaNO3·H20-5% of O, Zn (NO)3)2·6H2O in an amount of 0 to 1% by mass of the main component, tributyl borate in an amount of 0 to 1% by mass of the main component, and Ba (NO)3)2The dosage of the composition is 0-0.5% of the mass of the main component.
A preparation method of the medium-low-sintering-temperature stable type dielectric material comprises the following specific steps:
weighing the raw materials in the main component according to the proportion, dissolving bismuth nitrate pentahydrate in glacial acetic acid, dissolving sodium nitrate in deionized water, mixing the two, and adding the following components in parts by weight: citric acid 1: dissolving 1-4 weighed citric acid in deionized water, adjusting the pH value to 6-8 with ammonia water, and dropwise adding tetrabutyl titanate in a water bath stirring process at 80-90 ℃ to obtain a transparent solution A;
secondly, dissolving tributyl borate and tetraethyl silicate in nitric acid or acetic acid, adjusting the pH value to 2-4, and naming a solution 1; in Zn (NO)3)2·6H2Dissolving O in water or in Li2CO3Adding water and acetic acid to dissolve until no bubbles are generated, and naming a solution 2; adding water to dissolve in barium nitrate to name a solution 3; slowly pouring the mixture of the solution 1, the solution 2 and the solution 3 into a beaker of 100-500 ml, stirring for 0.5-4 hours by using a magnetic stirrer, and heating the beaker in a water bath kettle in a water bath manner at the heating temperature of 80-90 ℃ to obtain a solution B;
adding niobium hydroxide into the HF solution, and stirring in a water bath at 80 ℃ until the niobium hydroxide is completely dissolved to obtain a solution C; mixing BaTiO3Dissolving the powder in deionized water and ultrasonically preparing BaTiO for 1h3Continuously carrying out ultrasonic treatment on the suspension for 2 hours, sequentially dropwise adding the solution A, the solution B and the solution C, stirring in a water bath at 50 ℃ for 2-8 hours, drying the slurry in an oven at 100 ℃ for 24-48 hours, grinding, and carrying out heat treatment at 600-800 ℃ for 2-5 hours to obtain powder;
and fourthly, adding a polyvinyl alcohol aqueous solution accounting for 2.5-5 wt% of the weight of the obtained powder into the obtained powder for granulation, sieving the obtained powder through a 100-mesh sieve for dry pressing, carrying out glue discharging on the pressed green ceramic chip at the temperature of 600-650 ℃ for 2 hours, sintering the blank body subjected to glue discharging at the temperature of 800-1100 ℃ for 2-4 hours in a high-temperature furnace to obtain a compact ceramic sample, grinding and polishing the sample, carrying out phase analysis by using an X-ray diffractometer, coating silver paste on two surfaces of the sample, and carrying out silver burning at the temperature of 500-750 ℃ for 5-15 minutes to obtain the dielectric material.
Preferably, the HF solution is HF: deionized water 2: 8.
the invention has the following beneficial effects:
the dielectric ceramic prepared by the invention has the advantages of low sintering temperature, excellent temperature stability, cheap formula raw materials, simple preparation process, sintering temperature of 900 ℃, material room temperature dielectric constant of 896, room temperature dielectric loss of 0.019, temperature change rate of not more than +/-15% in the temperature range of-55-200 ℃, and room temperature resistivity of 6.5 multiplied by 1011Thus, the dielectric ceramic of the multilayer ceramic capacitor meets the requirement of the dielectric ceramic of the multilayer ceramic capacitor meeting the X9R characteristic.
Drawings
FIG. 1 is an SEM image of a dielectric material prepared by sintering in example 1.
Detailed Description
The following examples are included to provide further detailed description of the present invention and to provide those skilled in the art with a more complete, concise, and exact understanding of the principles and spirit of the invention.
Example 1: the medium-low-burning temperature stable dielectric material is prepared by the following method:
dissolving bismuth nitrate pentahydrate in glacial acetic acid, dissolving sodium nitrate in deionized water, mixing the two solutions, and mixing the two solutions according to the molar ratio of cation: citric acid 1: 3, dissolving citric acid weighed in deionized water, adjusting the pH value to 7 by using ammonia water, and dropwise adding tetrabutyl titanate in the stirring process of a water bath at the temperature of 85 ℃ to obtain a transparent solution A;
dissolving tributyl borate and tetraethyl silicate in nitric acid or acetic acid, adjusting the pH value to about 3 by using nitric acid (only 1 drop of nitric acid needs to be added), and naming solution 1; in Zn (NO)3)2·6H2Adding water into the O to dissolve, and naming solution 2; adding water to dissolve in barium nitrate to name a solution 3; slowly pouring the mixture of the solution 1, the solution 2 and the solution 3 into a beaker of 100-500 ml, stirring for 1 hour by using a magnetic stirrer, and putting the beaker into a water bath kettle to heat in a water bath at the heating temperature of 80-90 ℃ to obtain a solution B;
adding niobium hydroxide into an HF solution (the HF solution is HF:deionized water 2: 8) stirring in water bath at 80 ℃ until the mixture is completely dissolved to obtain a solution C; mixing BaTiO3Dissolving the powder in deionized water and ultrasonically preparing BaTiO for 1h3Continuously performing ultrasonic treatment on the suspension for 2 hours, sequentially dropwise adding the solution A, the solution B and the solution C, stirring in a water bath at 50 ℃ for 4 hours, drying the slurry in an oven at 100 ℃ for 36 hours, grinding, and performing heat treatment at 700 ℃ for 3.5 hours to obtain powder;
and fourthly, adding a polyvinyl alcohol aqueous solution with the weight of 5 wt% of the powder into the obtained powder for granulation, sieving the powder by a 100-mesh sieve, carrying out dry pressing for forming, carrying out gel discharging on the pressed green ceramic wafer at the temperature of 600 ℃ for 2 hours, sintering the gel-discharged green body at the temperature of 900 ℃ for 3 hours in a high-temperature furnace to obtain a compact ceramic sample, grinding and polishing the sample, coating silver paste on both surfaces of the sample, carrying out silver firing at the temperature of 500 ℃ for 10 minutes to obtain a dielectric material, and carrying out dielectric property testing.
The preparation principle of the invention is that different solution metal ions are coated around barium titanate powder to inhibit the growth of crystal grains, the average crystal grain is 300-400 nm (as shown in figure 1), relatively low sintering temperature can be obtained, and good temperature stability can be obtained. The proportion of the main component raw materials can adopt any number in the table 2.
Example 2: the medium-low-burning temperature stable dielectric material is prepared by the following method:
dissolving bismuth nitrate pentahydrate in glacial acetic acid, dissolving sodium nitrate in deionized water, mixing the two solutions, and mixing the two solutions according to the molar ratio of cation: citric acid 1: dissolving 1 weight of citric acid in deionized water, adjusting the pH value to 6 by using ammonia water, and dropwise adding tetrabutyl titanate in the water bath stirring process at the temperature of 80 ℃ to obtain a transparent solution A;
secondly, dissolving tributyl borate and tetraethyl silicate in nitric acid or acetic acid, and adjusting the pH value to about 2 by using acetic acid to name a solution 1; with Li2CO3Substitution of Zn (NO)3)2·6H2O in Li2CO3Adding water and acetic acid to dissolve until no bubbles are generated, and naming a solution 2; adding water to dissolve in barium nitrate to name a solution 3; slowly pouring the mixture of the solution 1, the solution 2 and the solution 3 into a beaker with the volume of 100-500 ml, and stirring by using a magnetic stirrerAfter 0.5 hour, putting the beaker into a water bath kettle to heat in a water bath, wherein the heating temperature is 80-90 ℃, and obtaining a solution B;
adding niobium hydroxide into an HF solution (HF solution is HF: deionized water: 2: 8), and stirring in a water bath at 80 ℃ until the niobium hydroxide is completely dissolved to obtain a solution C; mixing BaTiO3Dissolving the powder in deionized water and ultrasonically preparing BaTiO for 1h3Continuously performing ultrasonic treatment on the suspension for 2 hours, sequentially dropwise adding the solution A, the solution B and the solution C, stirring in a water bath at 50 ℃ for 2 hours, drying the slurry in an oven at 100 ℃ for 24 hours, grinding, and performing heat treatment at 600 ℃ for 5 hours to obtain powder;
and fourthly, adding a polyvinyl alcohol aqueous solution accounting for 2.5 wt% of the weight of the obtained powder into the obtained powder for granulation, sieving the obtained powder by a 100-mesh sieve, carrying out dry pressing and forming, carrying out gel discharging on the pressed green ceramic wafer at the temperature of 600 ℃ for 2 hours, sintering the gel-discharged green body at the temperature of 800 ℃ for 2 hours in a high-temperature furnace to obtain a compact ceramic sample, grinding and polishing the sample, carrying out phase analysis by using an X-ray diffractometer, coating silver paste on both sides of the sample, and carrying out silver firing at the temperature of 750 ℃ for 5 minutes to obtain the dielectric material. The proportion of the main component raw materials can adopt any number in the table 2.
Example 3: the medium-low-burning temperature stable dielectric material is prepared by the following method:
dissolving bismuth nitrate pentahydrate in glacial acetic acid, dissolving sodium nitrate in deionized water, mixing the two solutions, and mixing the two solutions according to the molar ratio of cation: citric acid 1: 4, dissolving citric acid weighed by a weight ratio of 4 in deionized water, adjusting the pH value to 8 by ammonia water, and dropwise adding tetrabutyl titanate in a water bath stirring process at 90 ℃ to obtain a transparent solution A;
secondly, dissolving tributyl borate and tetraethyl silicate in nitric acid or acetic acid, and adjusting the pH value to about 4 by using acetic acid to name a solution 1; in Zn (NO)3)2·6H2Adding water into the O to dissolve, and naming solution 2; adding water to dissolve in barium nitrate to name a solution 3; slowly pouring the mixture of the solution 1, the solution 2 and the solution 3 into a beaker of 100-500 ml, stirring for 4 hours by using a magnetic stirrer, and putting the beaker into a water bath kettle to heat in a water bath at the heating temperature of 80-90 ℃ to obtain a solution B;
thirdly, adding niobium hydroxide into HF solution (H)The solution F is HF: deionized water 2: 8) stirring in a water bath at 90 ℃ until the mixture is completely dissolved to obtain a solution C; mixing BaTiO3Dissolving the powder in deionized water and ultrasonically preparing BaTiO for 1h3Continuously performing ultrasonic treatment on the suspension for 2 hours, sequentially dropwise adding the solution A, the solution B and the solution C, stirring in a water bath at 50 ℃ for 8 hours, drying the slurry in an oven at 100 ℃ for 48 hours, grinding, and performing heat treatment at 800 ℃ for 2 hours to obtain powder;
and fourthly, adding polyvinyl alcohol aqueous solution with the weight of 3.5 wt% of the powder into the obtained powder for granulation, sieving the powder by a 100-mesh sieve, carrying out dry pressing for molding, carrying out gel discharging on the pressed green ceramic wafer at the temperature of 650 ℃ for 2 hours, sintering the gel-discharged green body at the temperature of 1100 ℃ for 4 hours in a high-temperature furnace to obtain a compact ceramic sample, grinding and polishing the sample, carrying out phase analysis by using an X-ray diffractometer, coating silver paste on both sides of the sample, and carrying out silver burning at the temperature of 600 ℃ for 15 minutes to obtain the dielectric material. The proportion of the main component raw materials can adopt any number in the table 2.
According to the method provided in the embodiment 1, the dielectric property test is carried out on the dielectric material prepared by adopting the main component raw material proportion in the table 2, and the test result is as follows:
TABLE 2 proportions of the respective main components
Figure BDA0003345137220000051
Note: the ratio of each component in Table 2 is BaTiO3The mass ratio of (a).
TABLE 3 Performance test results for different main component ratios
Figure BDA0003345137220000052
Figure BDA0003345137220000061
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical scheme according to the technical idea proposed by the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.

Claims (4)

1. A medium material with medium-low burning temperature stability is characterized in that the main component is BaTiO3The main component and Nb (OH)5、Cu(NO3)2、Ti(OC4O9)4、Bi(NO3)3·5H2O、NaNO3·H2O、Zn(NO3)2·6H2O、Ba(NO3)2The boric acid tributyl ester and the tetraethyl silicate are prepared by the steps of dissolving and sintering.
2. A mid-to-low firing temperature stable dielectric material as claimed in claim 1, wherein: said Nb (OH)5The dosage of the Cu (NO) accounts for 0.2 to 2 percent of the mass of the main component3)2The dosage of the Bi (NO) accounts for 0 to 15 percent of the mass of the main component3)2·5H2The dosage of O is 5 to 60 percent of the mass of the main component, and Ti (OC)4O9)4The dosage of the composition is 5 to 20 percent of the mass of the main component, the dosage of the tetraethyl silicate is 0 to 0.1 percent of the mass of the main component, and the NaNO3·H20-5% of O, Zn (NO)3)2·6H2O in an amount of 0 to 1% by mass of the main component, tributyl borate in an amount of 0 to 1% by mass of the main component, and Ba (NO)3)2The dosage of the composition is 0-0.5% of the mass of the main component.
3. The method for preparing the medium material with the low-sintering temperature stability as set forth in any one of claims 1-2 is characterized by comprising the following specific steps:
weighing the main components and other raw materials according to the proportion, dissolving bismuth nitrate pentahydrate in glacial acetic acid, dissolving sodium nitrate in deionized water, mixing the two, and adding the following raw materials according to the proportion of cations: citric acid 1: dissolving 1-4 weighed citric acid in deionized water, adjusting the pH value to 6-8 with ammonia water, and dropwise adding tetrabutyl titanate in a water bath stirring process at 80-90 ℃ to obtain a transparent solution A;
secondly, dissolving tributyl borate and tetraethyl silicate in nitric acid or acetic acid, adjusting the pH value to 2-4, and naming a solution 1; in Zn (NO)3)2·6H2Dissolving O in water or in Li2CO3Adding water and acetic acid to dissolve until no bubbles are generated, and naming a solution 2; adding water to dissolve in barium nitrate to name a solution 3; slowly pouring the mixture of the solution 1, the solution 2 and the solution 3 into a beaker of 100-500 ml, stirring for 0.5-4 hours by using a magnetic stirrer, and heating the beaker in a water bath kettle in a water bath manner at the heating temperature of 80-90 ℃ to obtain a solution B;
adding niobium hydroxide into the HF solution, and stirring in a water bath at 80 ℃ until the niobium hydroxide is completely dissolved to obtain a solution C; mixing BaTiO3Dissolving the powder in deionized water and ultrasonically preparing BaTiO for 1h3Continuously carrying out ultrasonic treatment on the suspension for 2 hours, sequentially dropwise adding the solution A, the solution B and the solution C, stirring in a water bath at 50 ℃ for 2-8 hours, drying the slurry in an oven at 100 ℃ for 24-48 hours, grinding, and carrying out heat treatment at 600-800 ℃ for 2-5 hours to obtain powder;
and fourthly, adding a polyvinyl alcohol aqueous solution accounting for 2.5-5 wt% of the weight of the obtained powder into the obtained powder for granulation, sieving the obtained powder through a 100-mesh sieve for dry pressing, carrying out glue discharging on the pressed green ceramic chip at the temperature of 600-650 ℃ for 2 hours, sintering the blank body subjected to glue discharging at the temperature of 800-1100 ℃ for 2-4 hours in a high-temperature furnace to obtain a compact ceramic sample, grinding and polishing the sample, carrying out phase analysis by using an X-ray diffractometer, coating silver paste on two surfaces of the sample, and carrying out silver burning at the temperature of 500-750 ℃ for 5-15 minutes to obtain the dielectric material.
4. The method for preparing a medium material with medium and low firing temperature stability as claimed in claim 3, wherein: the HF solution is HF: deionized water 2: 8.
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CN104291809A (en) * 2014-09-26 2015-01-21 天津大学 Preparation method of ultrahigh-temperature multi-layer ceramic capacitor medium
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