CN113831123B - Dielectric ceramic material for barium titanate-based chip capacitor and preparation method and application thereof - Google Patents

Dielectric ceramic material for barium titanate-based chip capacitor and preparation method and application thereof Download PDF

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CN113831123B
CN113831123B CN202111043568.8A CN202111043568A CN113831123B CN 113831123 B CN113831123 B CN 113831123B CN 202111043568 A CN202111043568 A CN 202111043568A CN 113831123 B CN113831123 B CN 113831123B
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dielectric ceramic
ceramic material
barium titanate
glass powder
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李少利
江俊俊
谢波
罗婷
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Chengdu Hongke Electronic Technology Co ltd
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Abstract

The invention provides a barium titanate-based dielectric ceramic material for chip capacitors, a preparation method and application thereof, and relates to the technical field of capacitor ceramic materials. Barium titanate-based dielectric ceramic material for chip capacitor, and BaTiO 3 The weight percentage of the additive is 100 percent, and the following components in percentage by weight are added: 0 to 1.70% of La 2 O 3 0 to 1.60% of Nb 2 O 5 0 to 0.40% of CeO 2 0 to 0.12% of MnO 2 、0~0.50%MgCO 3 And 0.3-1.3% of glass powder. The preparation method comprises the following steps: s1: mixing the glass powder components in proportion to prepare glass powder; s2: mixing the obtained glass powder and BaTiO 3 And mixing the rest components in proportion to prepare the dielectric ceramic material. The invention also provides a barium titanate-based dielectric ceramic material for chip capacitors, which is prepared by the method and is applied to the production of X7R-502 dielectric ceramics. The dielectric ceramic material for the barium titanate-based chip capacitor can be prepared, which has higher dielectric constant and smaller dielectric loss under 1MHz on the basis of meeting the temperature characteristic of X7R.

Description

Dielectric ceramic material for barium titanate-based chip capacitor and preparation method and application thereof
Technical Field
The invention relates to the technical field of capacitor ceramic materials, in particular to a barium titanate-based dielectric ceramic material for chip capacitors and a preparation method and application thereof.
Background
The chip capacitor has the advantages of small volume, stable electrical performance, high reliability and the like, and is suitable for a high-frequency electronic circuit of a gold wire bonding process; the supporting material for producing the chip capacitor needs to meet the conditions of high dielectric constant, low dielectric loss and the like under the condition of high frequency (1 MHz); the supporting material for producing the chip capacitor generally uses a dielectric ceramic material with X7R characteristics.
At present, the dielectric constant of the existing dielectric ceramic material with the X7R characteristic is low and generally difficult to reach 5000, the dielectric loss is also high, and the production requirement of the highest-end model product of the chip capacitor cannot be met.
Disclosure of Invention
The first purpose of the invention is to provide a dielectric ceramic material for barium titanate-based chip capacitors, which can have higher dielectric constant and smaller dielectric loss at 1MHz on the basis of meeting the temperature characteristic of X7R; the production requirement of the highest-end model product of the chip capacitor can be met.
The second purpose of the invention is to provide a preparation method of the dielectric ceramic material for the barium titanate-based chip capacitor, and the dielectric ceramic material for the barium titanate-based chip capacitor, which is prepared by the preparation method, has higher dielectric constant and smaller dielectric loss at 1 MHz.
The third purpose of the invention is to provide the application of the dielectric ceramic material for the barium titanate-based chip capacitor, which can be effectively applied to the production of X7R-502 dielectric ceramic.
The embodiment of the invention is realized by the following technical scheme:
barium titanate-based dielectric ceramic material for chip capacitor, and BaTiO 3 The weight percentage of the additive is 100 percent, and the following components in weight percentage are added: 0 to 1.70% of La 2 O 3 0 to 1.60% of Nb 2 O 5 0 to 0.40% of CeO 2 0 to 0.12% of MnO 2 、0~0.50% MgCO 3 And 0.3-1.3% of glass powder.
Further, the glass powder comprises the following components in percentage by weight: 10-20% of Nd 2 O 3 35 to 45 percent of ZnO and 15 to 25 percent of SiO 2 And 15-25% of B 2 O 3
The chip capacitor product can be applied to a high-frequency circuit, the dielectric loss of the dielectric ceramic material of a barium titanate system can be multiplied under 1MHz, the heating failure of the product can be caused, and in order to reduce the dielectric loss of the dielectric ceramic material under 1MHz, the barium titanate-based chip capacitor disclosed by the inventionSelecting corresponding components and content ratio by using a dielectric ceramic material, and adding a modified substance MnO into a main crystal phase system 2 、MgCO 3 And rare earth element (La) 3+ 、Nd 3+ ) Etc. can ensure BaTiO 3 Spontaneous polarization while inhibiting BaTiO 3 The crystal grains grow abnormally, the relaxation polarization caused by space charge polarization is reduced, a compact ceramic body structure is obtained, the dielectric constant of the dielectric ceramic material for the barium titanate-based chip capacitor reaches 5000, and the dielectric loss of the dielectric ceramic material for the barium titanate-based chip capacitor under high frequency (1 MHz) is reduced;
meanwhile, the glass powder formed by adding a certain component and content ratio into the dielectric ceramic material for the barium titanate-based chip capacitor can play a role in shifting peak pressure and also can play a role in mutually linking the components, so that the density of the dielectric ceramic material for the barium titanate-based chip capacitor is increased, the dielectric constant of the dielectric ceramic material for the barium titanate-based chip capacitor is increased, and the dielectric loss of the dielectric ceramic material for the barium titanate-based chip capacitor is reduced.
Further, BaTiO 3 The crystal form of (A) can change along with the change of temperature, so that the dielectric constant of the crystal form changes in a nonlinear way, the X7R characteristic is difficult to achieve within the temperature range of-55 to 125 ℃, and the crystal form is in a BaTiO state 3 In which Nd is introduced 2 O 3 、ZnO、SiO 2 And B 2 O 3 Glass powder of composition La 2 O 3 、CeO 2 、Nb 2 O 5 And SiO 2 Belongs to a peak shifting agent and a broadening agent, and enables BaTiO to be used without excessively inhibiting the ferroelectricity thereof 3 The Curie peak is dispersed and moves to the middle part, so that the dielectric constant is high and smooth; the dielectric ceramic material for the barium titanate-based chip capacitor has the dielectric constant of more than 5000, and simultaneously, the change rate of capacitance along with temperature is optimized, so that the X7R characteristic is achieved.
The preparation method of the dielectric ceramic material for the barium titanate-based chip capacitor comprises the following steps:
s1: mixing the components of the glass powder in proportion to prepare the glass powder;
s2: the prepared glassPowder and BaTiO 3 And mixing the rest components in proportion to prepare the dielectric ceramic material.
Further, Nd is added in step S1 2 O 3 、ZnO、SiO 2 And B 2 O 3 Mixing according to a ratio, sieving for 4-5 times by using a 200-mesh sieve, placing in a zirconia sagger, calcining at 900-970 ℃, grinding for 1-2 hours by using deionized water as a medium by using a stirring mill, drying at 100-140 ℃, and sieving by using a 200-mesh sieve to obtain the glass powder.
Further, the glass frit and BaTiO prepared in the step S2 3 、CeO 2 、La 2 O 3 、Nb 2 O 5 、MnO 2 、MgCO 3 Adding the vertical vibration mill in sequence from large to small according to the proportion, and mixing the following raw materials: deionized water: and (3) vibrating and grinding the ball-milling medium =1:1.4:5 for 15-20 h in mass ratio, processing the ground material through a 320-mesh sieve to obtain ceramic slurry, drying the ceramic slurry at 100-140 ℃, and sieving the ceramic slurry through a 200-mesh sieve to obtain the dielectric ceramic material.
A dielectric ceramic material for a barium titanate-based chip capacitor is applied to production of X7R-502 dielectric ceramic, the prepared dielectric ceramic material is added with 7-8 wt% of paraffin for granulation, a hydraulic press is used for preparing a wafer with the diameter of 15mm and the thickness of 1.3-1.7 mm, then the temperature is increased to 450 ℃ at the speed of 1.5 ℃/min to discharge the paraffin, then the temperature is increased to 1350-1390 ℃ at the speed of 3 ℃/min to be sintered for 3h and then cooled with a furnace, and the X7R-502 dielectric ceramic is prepared.
The technical scheme of the embodiment of the invention at least has the following advantages and beneficial effects:
1. the dielectric ceramic material for the barium titanate-based chip capacitor is prepared from corresponding components in percentage by weight, has a high dielectric constant of more than 5000 on the basis of reaching the X7R characteristic, and has low dielectric loss at high frequency (1 MHz).
2. The invention can prepare the dielectric ceramic material for the barium titanate-based chip capacitor with higher dielectric constant and smaller dielectric loss under 1 MHz.
3. The dielectric ceramic material for the barium titanate-based chip capacitor, which is prepared by the invention, has higher dielectric constant and smaller dielectric loss at 1MHz, can be applied to producing X7R-502 dielectric ceramic.
4. The dielectric ceramic material for the barium titanate-based chip capacitor does not select toxic and harmful substances such as Pb, Cr, Hg and the like, and meets the environmental protection requirement of European Union ROHS instruction.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the dielectric ceramic material prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The dielectric ceramic material for barium titanate-based chip capacitors provided by the embodiments of the present invention, and the preparation method and application thereof are specifically described below.
Examples 1 to 10
Examples 1 to 10 provide barium titanate-based dielectric ceramic materials for chip capacitors, and BaTiO 3 The weight percentage of the additive is 100%, and the weight percentage of the components added is shown in table 1 and table 2.
TABLE 1 glass frit compositions
Figure DEST_PATH_IMAGE001
TABLE 2 barium titanate-based dielectric ceramic Material composition for chip capacitors
Figure 189816DEST_PATH_IMAGE002
Figure DEST_PATH_IMAGE003
Embodiments 1 to 10 further provide a method for preparing a dielectric ceramic material for a barium titanate-based chip capacitor, including the steps of:
s1: adding Nd 2 O 3 、ZnO、SiO 2 And B 2 O 3 Mixing according to a ratio, sieving for 4-5 times by using a 200-mesh sieve, placing in a zirconia sagger, calcining at 900-970 ℃, grinding for 1-2 hours by using a stirring mill by using deionized water as a medium, drying at 100-140 ℃, and sieving by using a 200-mesh sieve to obtain glass powder;
s2: mixing the obtained glass powder and BaTiO 3 、CeO 2 、La 2 O 3 、Nb 2 O 5 、MnO 2 、MgCO 3 Adding the vertical vibration mill in sequence from large to small according to the proportion, and mixing the following powder: deionized water: and (3) vibrating and grinding the ball-milling medium =1:1.4:5 for 15-20 h in mass ratio, processing the ground material through a 320-mesh sieve to obtain ceramic slurry, drying the ceramic slurry at 100-140 ℃, and sieving the ceramic slurry through a 200-mesh sieve to obtain the dielectric ceramic material. The Scanning Electron Microscope (SEM) image of the dielectric ceramic material prepared in example 1 is shown in FIG. 1.
The embodiment 1 to 10 also provides application of the dielectric ceramic material for the barium titanate-based chip capacitor in producing X7R-502 dielectric ceramic, the prepared dielectric ceramic material is added with 7 to 8wt% of paraffin for granulation, a hydraulic press is used for preparing a wafer with the diameter of 15mm and the thickness of 1.3 to 1.7mm, then the temperature is increased to 450 ℃ at the speed of 1.5 ℃/min for discharging paraffin, then the temperature is increased to 1350 to 1390 ℃ at the speed of 3 ℃/min for sintering for 3h, and furnace cooling is carried out to prepare the X7R-502 dielectric ceramic.
Comparative examples 1 to 8
Comparative examples 1 to 8 provide a dielectric ceramic material comprising BaTiO 3 The weight percentage of (b) is 100%, and the components added in weight percentage are shown in table 3 and table 4.
TABLE 3 glass frit compositions
Figure 654426DEST_PATH_IMAGE004
TABLE 4 dielectric ceramic Material composition
Figure DEST_PATH_IMAGE005
The preparation method of the dielectric ceramic material provided in the comparative examples 1 to 8 is the same as that of the examples 1 to 10, and the dielectric ceramic is prepared by the preparation method of the examples 1 to 10.
Experimental example 1
The dielectric properties of X7R-502 dielectric ceramics A1, A2 and A3 prepared in example 1 at sintering temperatures of 1350 ℃, 1370 ℃ and 1390 ℃ respectively and the dielectric ceramics B1, B2 and B3 prepared in American FerroX7R-502 at sintering temperatures of 1350 ℃, 1370 ℃ and 1390 ℃ respectively were tested by a dielectric temperature spectrometer, and the results are shown in Table 5.
TABLE 5 dielectric Property Table
Figure 27639DEST_PATH_IMAGE006
As can be seen from Table 5, the dielectric constant of the X7R-502 dielectric ceramic prepared by the invention is higher than that of the dielectric ceramic of FerroX7R-502 in the United states and is more than 5000; the dielectric loss is less than that of the dielectric ceramic of FerroX7R-502 in the United states, the dielectric loss of the dielectric ceramic is less than 0.6% under 1KHz, and the dielectric loss is less than 1.8% under 1 MHz; the change rate of the capacitance along with the temperature is small within the temperature range of-55 to 125 ℃, and the temperature characteristic of X7R is met.
Experimental example 2
The dielectric properties of the X7R-502 dielectric ceramics prepared in examples 1-10 and the dielectric ceramics prepared in comparative examples 1-8 were measured by a dielectric temperature spectrometer, and the results are shown in Table 6.
TABLE 6 dielectric Property Table
Figure DEST_PATH_IMAGE007
As can be seen from table 6, the dielectric ceramic material of comparative example 1 has no glass frit, the dielectric ceramic material of comparative example 2 has no glass frit and has different components, the dielectric ceramic material of comparative example 3 has no glass frit and has different components, the dielectric ceramic material of comparative example 4 has different components of glass frit, the dielectric ceramic material of comparative example 5 has different components, and the dielectric ceramic materials of comparative examples 6 to 8 have different content ratios of the components; the dielectric ceramic X7R-502 prepared from the dielectric ceramic material provided by the invention has high dielectric constant which is higher than 5000; the dielectric loss is small, the dielectric loss of the dielectric ceramic is less than 0.6% under 1KHz, and the dielectric loss is less than 1.8% under 1 MHz; the change rate of the capacitance along with the temperature is small within the temperature range of-55 to 125 ℃, and the temperature characteristic of X7R is met.
In conclusion, the dielectric ceramic material for the barium titanate-based chip capacitor, which is provided by the application, has the advantages that the prepared X7R-502 dielectric ceramic has higher dielectric constant and smaller dielectric loss under 1MHz on the basis of meeting the temperature characteristic of X7R; the production requirement of the highest-end model product of the chip capacitor can be met.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The barium titanate-based dielectric ceramic material for chip capacitor is characterized by comprising BaTiO 3 The weight percentage of the additive is 100 percent, and the following components in percentage by weight are added: 0.61-1.70% of La 2 O 3 0.54 to 1.60% of Nb 2 O 5 0.05 to 0.40 percent of CeO 2 0.08 to 0.12% of MnO 2 、0.03~0.50% MgCO 3 And 0.3-1.3% of glass powder.
2. The barium titanate-based dielectric ceramic material for chip capacitors as claimed in claim 1, wherein said glass powder comprises the following components in percentage by weight: 10-20% of Nd 2 O 3 35 to 45 percent of ZnO and 15 to 25 percent of SiO 2 And 15-25% of B 2 O 3
3. The barium titanate-based dielectric ceramic material for chip capacitors as claimed in claim 2, wherein the glass powder comprises the following components in percentage by weight: 16% Nd 2 O 3 42% of ZnO, 18% of SiO 2 And 24% of B 2 O 3
4. The barium titanate-based dielectric ceramic material for chip capacitors as claimed in claim 2, wherein said glass powder comprises the following components in percentage by weight: 13% of Nd 2 O 3 40% of ZnO, 24% of SiO 2 And 23% of B 2 O 3
5. The barium titanate-based dielectric ceramic material for chip capacitors as claimed in any one of claims 1 to 4, wherein BaTiO is used as the dielectric ceramic material 3 The weight percentage of the additive is 100 percent, and the following components in percentage by weight are added: 0.61% of La 2 O 3 0.54% of Nb 2 O 5 0.05% of CeO 2 0.09% MnO 2 、0.03% MgCO 3 And 0.5% of glass powder.
6. The barium titanate-based dielectric ceramic material for chip capacitors as claimed in any one of claims 1 to 4, wherein BaTiO is used as the dielectric ceramic material 3 The weight percentage of the additive is 100 percent, and the following components in percentage by weight are added: 0.87% of La 2 O 3 0.9% of Nb 2 O 5 0.34% of CeO 2 0.11% MnO 2 、0.28% MgCO 3 And 0.8% of glass powder.
7. A preparation method of the dielectric ceramic material for the barium titanate-based chip capacitor as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
s1: mixing the components of the glass powder in proportion to prepare the glass powder;
s2: mixing the obtained glass powder and BaTiO 3 And the restThe dielectric ceramic material is prepared by mixing the components in proportion.
8. The method for preparing a dielectric ceramic material for barium titanate-based chip capacitors as claimed in claim 7, wherein said step S1 is carried out by adding Nd 2 O 3 、ZnO、SiO 2 And B 2 O 3 Mixing according to a ratio, sieving for 4-5 times by using a 200-mesh sieve, placing in a zirconia sagger, calcining at 900-970 ℃, grinding for 1-2 hours by using deionized water as a medium by using a stirring mill, drying at 100-140 ℃, and sieving by using a 200-mesh sieve to obtain the glass powder.
9. The method for preparing a dielectric ceramic material for barium titanate-based chip capacitors as claimed in claim 7, wherein said step S2 comprises mixing the glass powder with BaTiO 3 、CeO 2 、La 2 O 3 、Nb 2 O 5 、MnO 2 、MgCO 3 Adding the vertical vibration mill in sequence from large to small according to the proportion, and mixing the following raw materials: deionized water: and (3) vibrating and grinding the ball-milling medium =1:1.4:5 for 15-20 h in mass ratio, processing the ground material through a 320-mesh sieve to obtain ceramic slurry, drying the ceramic slurry at 100-140 ℃, and sieving the ceramic slurry through a 200-mesh sieve to obtain the dielectric ceramic material.
10. Use of the barium titanate-based dielectric ceramic material for chip capacitors as claimed in any one of claims 1 to 6 or the barium titanate-based dielectric ceramic material for chip capacitors as claimed in any one of claims 7 to 9 in the production of X7R-502 dielectric ceramic.
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