CN114133238B - Ceramic dielectric material and preparation method and application thereof - Google Patents

Ceramic dielectric material and preparation method and application thereof Download PDF

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CN114133238B
CN114133238B CN202111287248.7A CN202111287248A CN114133238B CN 114133238 B CN114133238 B CN 114133238B CN 202111287248 A CN202111287248 A CN 202111287248A CN 114133238 B CN114133238 B CN 114133238B
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ceramic dielectric
batio
ceramic
dielectric material
component
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CN114133238A (en
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邱基华
陈烁烁
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Guangdong Advanced Ceramic Material Technology Co ltd
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Guangdong Advanced Ceramic Material Technology Co ltd
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Abstract

The invention discloses a ceramic dielectric material and a preparation method and application thereof, wherein the ceramic dielectric material comprises BaTiO as a raw material 3 And a Zr-containing perovskite. The ceramic dielectric material of the invention is added with Zr-containing calcium titanium mineral substance which has high toughness and high bending strength and is mixed with BaTiO 3 Has good lattice matching property and can better match with BaTiO 3 The solid solution together can ensure that the electrical performance of the MLCC is not affected while improving the strength and the bending resistance of the MLCC, and can ensure that the MLCC has excellent durability.

Description

Ceramic dielectric material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electronic ceramic components, in particular to a ceramic dielectric material and a preparation method and application thereof.
Background
In recent years, electronic products such as notebook computers, satellite communication, smart phones and wearable devices have been rapidly developed, MLCCs (multilayer chip ceramic capacitors) have also been rapidly developed as a basic circuit electronic component, and market demands have become greater and greater.
The MLCC is an integral component formed by alternately laminating ceramic materials and metal materials together, and then laminating and co-firing the ceramic materials, wherein the ceramic materials mainly comprise ABO 3 Of ceramic material (mainly BaTiO) 3 ) Its advantages are high toughness and brittleness, and low bending resistance. One problem that often occurs during the use of MLCC products: in the process of welding the MLCC product on the circuit board, the MLCC is easily subjected to the action of bending mechanical stress, and the situations of cracking, failure and the like occur.
ZrO 2 The ceramic material has the characteristics of high strength, high toughness, high bending strength and the like, and if the ceramic material is mixed into MLCC, the cracking problem is expected to be improved, but if ZrO is directly mixed 2 The ceramic is added into the ceramic material as a bending-resistant reinforcing component, and the electricity of the MLCC product can be generatedThe performance is reduced.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a ceramic dielectric material which can improve the bending strength and the bending resistance of ceramic electronic components such as MLCC and the like, and does not influence the electrical performance.
Meanwhile, the invention also provides a preparation method and application of the ceramic dielectric material.
The first aspect of the invention provides a ceramic dielectric material, and the raw material of the ceramic dielectric material comprises BaTiO 3 And a Zr-containing perovskite.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention relates to the incorporation of Zr-containing perovskite into ceramic dielectric materials for ceramic components, such as MLCC, which have ZrO 2 High toughness and high bending strength of the material, but no ZrO 2 Has a low dielectric constant and is made of BaTiO 3 Poor lattice matching and difficulty in matching with BaTiO 3 Disadvantages of solid solution and doping, with BaTiO 3 Has good lattice matching property and can better match with BaTiO 3 The solid solution is carried out, so that the electric performance of the MLCC is not affected while the strength and the bending resistance of the MLCC are improved.
In some embodiments of the invention, the Zr-containing perovskite mineral has the formula AZrO 3 Said AZrO 3 A in (b) includes at least one of Ba and Ca.
In some embodiments of the invention, the Zr-containing perovskite is BaTiO 3 1% to 5%, preferably 1% to 4.5%, more preferably 2% to 4%. By controlling the addition amount of the Zr-containing calcium titanium mineral, the electrical property of the MLCC can be ensured not to be influenced.
In some embodiments of the present invention, the ceramic dielectric material further comprises a component a comprising MgO, MgCO 3 、Mg 2 (OH) 2 CO 3 At least one of (1). The molar weight of the component a is BaTiO 3 1% to 4%, preferably 1.3 to 3.5 percent. The component a can inhibit abnormal growth of crystal grains, and obtain higher resistivity and better TCC (temperature change rate).
In some embodiments of the invention, the feedstock for the ceramic dielectric material further comprises component b, which comprises MnCO 3 、MnO 2 、Mn 3 O 4 At least one of (1). The molar weight of the component b is BaTiO 3 0.01 to 0.5%, preferably 0.05 to 0.25%. The component b can enable the multilayer ceramic capacitor with low reduction resistance to obtain higher insulation resistance and reduce the formation of oxygen vacancies in the product during sintering.
In some embodiments of the present invention, the ceramic dielectric material further comprises a component c comprising Al as a raw material 2 O 3 、Cr 2 O 3 、V 2 O 5 At least one of (1). The molar weight of the component c is BaTiO 3 0.1% to 1%, preferably 0.3% to 0.9%, more preferably 0.38% to 0.88%. The component c can reduce oxygen vacancy formed in the sintering process of the product to a certain extent, and has a certain sintering assisting effect, so that the compactness of the product is improved.
In some embodiments of the invention, the feedstock material for the ceramic dielectric material further comprises a component rare earth oxide. The molar weight of the rare earth oxide is BaTiO 3 1% to 4%, preferably 1.5% to 3.5%.
In some embodiments of the invention, the rare earth oxide comprises an oxide of at least one of Y, Er, Ho, Dy.
In some embodiments of the present invention, the raw material of the ceramic dielectric material further comprises a sintering aid, and the molar amount of the sintering aid is BaTiO 3 0.5% to 3%, preferably 0.8% to 2%.
In some embodiments of the invention, the sintering aid comprises SiO 2 Or SiO 2 And BaO and CaO.
In some embodiments of the present invention, the raw materials of the ceramic dielectric material further comprise a dispersant, a binder, a plasticizer, and a solvent.
In the inventionIn some embodiments, the dispersant is BaTiO in mass 3 0.5 to 1% of the total amount of the active carbon.
In some embodiments of the invention, the binder is BaTiO in mass 3 7 to 10 percent of the total weight of the composition.
In some embodiments of the invention, the plasticizer is BaTiO 3 2 to 4 percent of the total weight of the composition.
In some embodiments of the invention, the solvent is BaTiO 3 70 to 100 percent of the total weight of the composition.
In some embodiments of the present invention, the dispersant, the binder, the plasticizer, and the solvent may be raw materials commonly used in the art, for example, the dispersant may include at least one of polyesteramide salt and triethanolamine, the binder may include at least one of polyvinylbutyral resin and ethylcellulose resin, the plasticizer may include at least one of dibutyl phthalate and polyethylene glycol, and the solvent may include at least one of toluene, absolute ethanol, methyl ethyl ketone, and isopropyl alcohol.
The second aspect of the present invention provides a method for preparing the ceramic dielectric material, comprising the following steps: and mixing the raw materials of the ceramic dielectric material to obtain the ceramic dielectric material.
In some embodiments of the present invention, the mixing step includes a grinding and dispersing step, and the grinding and dispersing step forms a slurry-like ceramic dielectric material.
In a third aspect of the present invention, a ceramic capacitor is provided, which includes a ceramic dielectric layer, and the ceramic dielectric layer is formed by sintering the ceramic dielectric material.
In some embodiments of the present invention, the ceramic capacitor is a semiconductor ceramic capacitor, a high voltage ceramic capacitor or an MLCC (multilayer chip ceramic capacitor), preferably an MLCC.
In some embodiments of the invention, the sintering temperature is 1000 to 1500 ℃, preferably 1100 to 1300 ℃. The sintering time is 1-3 h (such as 1.5h, 2h, 2.5h and the like).
In some embodiments of the invention, the sintering is at N 2 In a protective reducing atmosphere. The reducing atmosphere contains H 2 Said H is 2 The volume ratio of (A) is 0.5-2.5%.
The fourth aspect of the present invention provides a method for preparing an MLCC, comprising the steps of:
forming a film from the ceramic dielectric material to obtain a ceramic dielectric layer;
forming an inner electrode layer on the surface of the ceramic dielectric layer;
laminating, laminating and sintering a plurality of ceramic dielectric layers with inner electrode layers formed on the surfaces to obtain a ceramic chip;
and preparing electrodes at two ends of the ceramic chip to obtain the MLCC.
In some embodiments of the invention, the sintering temperature is 1000 to 1500 ℃, preferably 1100 to 1300 ℃. The sintering time is 1-3 h.
In some embodiments of the invention, the sintering is at N 2 In a protective reducing atmosphere. The reducing atmosphere contains H 2 Said H is 2 The volume ratio of (A) is 0.5-2.5%.
In some embodiments of the present invention, the step of binder removal before sintering is further included, that is, the pressed sample is subjected to a heat treatment, so that the binder, plasticizer, and the like in the ceramic dielectric material are burned and removed. The temperature of the heat treatment is 250-350 ℃, and the heat treatment can be carried out in an atmospheric atmosphere.
In some embodiments of the present invention, the method for forming the internal electrode layer on the surface of the ceramic dielectric layer may use a method commonly used in the art, for example, printing an internal electrode paste on the surface of the ceramic dielectric layer to form the internal electrode layer. The thickness of the inner electrode layer and the inner electrode slurry can be selected according to actual needs.
In some embodiments of the present invention, the electrodes prepared at both ends of the ceramic chip can be electrodes commonly used in the art, such as copper electrodes or Ni-plated, Sn-plated copper electrodes, and the thickness thereof can be selected according to actual needs.
Compared with the prior art, the invention has the following beneficial effects:
the ceramic dielectric material of the invention is added with Zr-containing calcium titanium mineral substance which has high toughness and high bending strength and is mixed with BaTiO 3 Has good lattice matching property and can better match with BaTiO 3 The solid solution is carried out, so that the electric performance of the MLCC can be ensured not to be influenced while the strength and the bending resistance of the MLCC are improved, and the MLCC can have excellent durability.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples. The starting materials used in the following examples, unless otherwise specified, are available from conventional commercial sources; the processes used, unless otherwise specified, are conventional in the art.
A ceramic dielectric material comprises BaTiO as main ingredient 3 According to BaTiO 3 The compound also contains other raw materials in the following proportion shown in the table 1, wherein the mol percentage of the compound is 100 percent:
TABLE 1 raw materials and mol percents of ceramic dielectric materials
Figure BDA0003333362050000041
Figure BDA0003333362050000051
In addition, the raw materials of the ceramic dielectric materials of the examples and the comparative examples also comprise BaTiO 3 0.5% by mass of a dispersant polyesteramide salt, based on BaTiO 3 Adhesive PVB accounting for 7.0 percent of the mass and BaTiO 3 3% by mass of a plasticizer polyethylene glycol and BaTiO 3 80% by mass of a solvent (toluene and anhydrous ethanol, m: m is 1.0 to 1.5).
The ceramic dielectric material is applied to the preparation of MLCC, and comprises the following steps:
(1) mixing BaTiO 3 Adding the components a, b and c, the sintering aid, the rare earth oxide, the dispersant, the binder, the plasticizer and the solvent into a sand mill, and performing sand milling dispersion to form the stableAnd (5) slurry with good quality.
(2) And casting the ceramic slurry to form a layer of film, and drying to obtain the ceramic dielectric layer with the thickness of 14 microns.
(3) And (3) forming a nickel inner electrode layer with the thickness of 2 microns on the surface of the ceramic dielectric layer obtained in the step (2) through a printing process.
(4) And laminating the ceramic dielectric layers printed with the internal electrodes, and pressing the laminated ceramic dielectric layers into a block. Pressing and cutting into a green blank with a certain size.
(5) Rubber discharging: and (3) carrying out glue discharging on the cut green blank in an air glue discharging box at 280 ℃ for 45 h.
(6) And (3) sintering: then in N 2 Protected H 2 Sintering for 2h at 1300 ℃ in the atmosphere to obtain the ceramic chip.
(5) Coating external electrode Cu slurry on two end surfaces of the ceramic chip, and baking at 860 ℃ to form external metal electrodes;
(6) and electroplating a layer of Ni and Sn on the surface of the Cu end through an electroplating process to obtain the MLCC.
The following method is adopted to detect each performance of the MLCC.
(1) Breaking strength: and testing by adopting a tension tester, fixing the product on a grinding tool of a test bench, and applying pressure of 1mm/s to the product by using the tension tester until the product is broken.
(2) Bending strength: and testing by adopting a tension tester, welding the product on the special PCB, reversely applying pressure of 1mm/s to the PCB until the volume change rate of the product is more than 10%, and recording the pressing distance (mm). The larger the pressing distance is, the stronger the bending resistance is.
(3) Capacity (Cp) and loss (Df): the capacity (Cp) and the loss (Df) are tested by adopting a capacity meter (KEYSIGHT model E4981A), setting the voltage to be 1V, testing the frequency to be 1KHz by X7R and testing the capacity (Cp) and the loss (Df) at the room temperature of 25 ℃.
(4) Insulation Resistance (IR): testing by using a resistance meter (agilent model 4339B) under the test conditions of 0603X7R104K 500C: the 50V charge was 60s and the IR value was recorded.
(5) Breakdown voltage (BDV): and testing by adopting a voltage withstanding tester (YD9811A), setting the boosting speed to be 6000V/30s, and recording the voltage of the product during breakdown.
(6) Durability: number 10000, temperature: 125 ℃, voltage: and (5) recording the number of MLCC failures after 1 time of rated voltage and 1000 hours of time.
The test results are shown in table 2 below:
TABLE 2 MLCC Performance test results
Figure BDA0003333362050000061
As can be seen from example 3 and comparative examples 1 and 2, AZrO, a flex-resistant reinforcing component 3 When the amount added was too small or not, the flexural strength and bending strength of the MLCC were very low, wherein the flexural strength and bending strength of comparative example 2 were comparable to those without AZrO addition 3 Comparative example 1 was improved but still significantly less than example 3, as demonstrated in AZrO 3 The addition of (2) can improve the flexural strength and the bending strength of the MLCC, but when the addition amount is too small, the effect of improving the flexural strength and the bending strength is difficult to be achieved, and the cracking failure and the like of a product are easily caused in the using process.
As can be seen by comparing example 4 with comparative example 3, when AZrO is used 3 When the amount of the additive is excessively added, the capacity of the product is affected due to the low dielectric constant of the additive; in addition, when the bending-resistant reinforcing component is added in excess, it is difficult to completely dissolve the BaTiO into the matrix 3 Thereby affecting the life of the product.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (4)

1. A ceramic dielectric material, characterized by: the ceramic dielectric material comprises BaTiO 3 The material comprises Zr-containing calcium titanium mineral, a component a, a component b, a component c, rare earth oxide and sintering aid;
the chemical formula of the Zr-containing calcium titanium mineral is AZrO 3 Said AZrO 3 A in (A) includes at least one of Ba and Ca; the molar weight of the Zr-containing calcium titanium mineral is BaTiO 3 1% -5%;
the component a comprises MgO and MgCO 3 、Mg 2 (OH) 2 CO 3 The molar amount of the component a is BaTiO 3 1% -4% of the total weight of the composition;
the component b comprises MnCO 3 、MnO 2 、Mn 3 O 4 At least one of (a), the molar amount of the component b is BaTiO 3 0.01 to 0.5 percent of;
the component c comprises Al 2 O 3 、Cr 2 O 3 、V 2 O 5 At least one of (1), the molar amount of the component c is BaTiO 3 0.1% -1%;
the molar weight of the rare earth oxide is BaTiO 3 1% -4% of the total weight of the composition;
the sintering aid comprises SiO 2 Or SiO 2 With BaO and CaO, the molar weight of the sintering aid is BaTiO 3 0.5% -3%.
2. The method for preparing the ceramic dielectric material according to claim 1, wherein: the method comprises the following steps: and mixing the raw materials of the ceramic dielectric material to obtain the ceramic dielectric material.
3. A ceramic capacitor, characterized by: the ceramic capacitor comprises a ceramic dielectric layer, wherein the ceramic dielectric layer is formed by sintering the ceramic dielectric material of claim 1.
4. A preparation method of a multilayer chip ceramic capacitor is characterized by comprising the following steps: the method comprises the following steps:
forming a film from the ceramic dielectric material of claim 1 to obtain a ceramic dielectric layer;
forming an inner electrode layer on the surface of the ceramic dielectric layer;
laminating, laminating and sintering a plurality of ceramic dielectric layers with inner electrode layers formed on the surfaces to obtain a ceramic chip;
and preparing electrodes at two ends of the ceramic chip to obtain the multilayer chip ceramic capacitor.
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