CN116425528A - Dielectric ceramic material and chip type multilayer ceramic capacitor prepared from same - Google Patents

Dielectric ceramic material and chip type multilayer ceramic capacitor prepared from same Download PDF

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CN116425528A
CN116425528A CN202310453123.XA CN202310453123A CN116425528A CN 116425528 A CN116425528 A CN 116425528A CN 202310453123 A CN202310453123 A CN 202310453123A CN 116425528 A CN116425528 A CN 116425528A
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barium titanate
rod
mol
ceramic
batio
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CN116425528B (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 belongs to the field of dielectric ceramics, and particularly relates to a dielectric ceramic material and a chip type multilayer ceramic capacitor prepared from the same. The dielectric ceramic material comprises the following components in percentage by mole: 5-35% of rod-shaped barium titanate, 0.1-5% of magnesium oxide, 0.1-2% of aluminum oxide, 1-5% of silicon oxide, 0.5-4.5% of rare earth additive, 0.05-0.6% of valence-changing element additive and the balance of spherical barium titanate. The invention increases the intensity of the ceramic medium by introducing the rod-shaped barium titanate particles, and ensures that the MLCC product has good mechanical property, electrical property and temperature stability by regulating and controlling the content and length-diameter ratio of the constituent components, rheological property of the ceramic slurry, casting process and sintering process.

Description

Dielectric ceramic material and chip type multilayer ceramic capacitor prepared from same
Technical Field
The invention belongs to the field of ceramics, and particularly relates to a dielectric ceramic material and a chip type multilayer ceramic capacitor prepared from the dielectric ceramic material.
Background
Multilayer ceramic capacitors (MLCCs) are widely used in communication infrastructure circuits in the fields of communication equipment, automotive electronics, industrial machines, medical appliances, etc., and can be used as power bypass capacitors such as liquid crystal modules (liquid crystal driving voltage lines), LSI/IC/OP amplifiers with high power supply voltage, or as smoothing capacitors such as DC-DC converters (input and output), switching power supplies (secondary side), etc.
Barium titanate (BaTiO) 3 ) Is a common matrix material in MLCC and has higher dielectric constant. When barium titanate is applied to an MLCC, barium titanate powder is generally prepared into slurry, cast into a membrane, and then subjected to electrode printing, lamination, pressing and cutting to form a green body with a certain shape and size, and then sintered into porcelain. However, barium titanate ceramics manufactured in this manner generally suffer from relatively poor bending resistance, and any operation that may cause bending deformation during device assembly and use may lead to cracking of the device ceramic body, thereby resulting in failure of the MLCC product. And if the mechanical property of the barium titanate ceramic is increased by adding certain auxiliary agents, the ceramic prepared by the method cannot achieve both good electrical property and temperature stability.
Therefore, there is still a need to find a barium titanate ceramic material with good mechanical properties, electrical properties and temperature stability.
Disclosure of Invention
Aiming at the problem that the prior art relates to barium titanate ceramics with poor mechanical properties, the invention provides a dielectric ceramic material and a chip type multilayer ceramic capacitor prepared from the dielectric ceramic material.
In order to achieve the above purpose, the method specifically comprises the following technical scheme:
in a first aspect, the present invention provides a dielectric ceramic material comprising the following components in mole percent: 5-35% of rod-shaped barium titanate, 0.1-5% of magnesium oxide, 0.1-2% of aluminum oxide, 1-5% of silicon oxide, 0.5-4.5% of rare earth additive, 0.05-0.6% of valence-changing element additive and the balance of spherical barium titanate;
the rare earth elements in the rare earth additive comprise at least one of Dy, ho, Y, yb, la, ce, er, gd; the valence-changing element in the valence-changing element additive comprises at least one of Mn, V, cr, mo.
The spherical barium titanate is barium titanate with spherical or quasi-spherical particle morphology, and the rod-shaped barium titanate is barium titanate with rod-shaped or quasi-rod-shaped particle morphology.
The main component of the dielectric ceramic material is spherical BaTiO 3 Also comprises a rod-like shapeBaTiO 3 The sintering aid, the rare earth element additive and the valence-variable element additive are taken as minor components. The existence of the rod-shaped particles is similar to a fiber structure, so that crack propagation can be effectively prevented, the strength of the porcelain body is improved, and the bending strength of the MLCC product is improved. MgO, al 2 O 3 And SiO 2 Forming liquid phase at high temperature to promote sintering densification of the blank body, and coating rod-shaped BaTiO with the liquid phase 3 The length is increased, and the bending strength of the product is further improved; rare earth elements are dissolved into BaTiO during sintering 3 A core-shell structure is formed, so that the temperature characteristic of the product is improved; the valence-changing element is beneficial to improving the anti-reduction capability in the sintering process of the porcelain body and reducing oxygen vacancies in the reducing atmosphere, thereby improving the reliability of the product.
As a preferred embodiment of the present invention, the dielectric ceramic material comprises the following components in mole percent: 5-35% of rod-shaped barium titanate, 0.3-3% of magnesium oxide, 0.5-1.5% of aluminum oxide, 2-3.5% of silicon oxide, 1-2% of rare earth additive, 0.1-0.3% of valence-changing element additive and the balance of spherical barium titanate.
Control rod-like BaTiO 3 When the addition amount of (c) is within the above range, the ceramic body strength, dielectric constant and temperature stability characteristics of the ceramic material of the present invention can be further ensured; rod-shaped BaTiO 3 When the addition amount is small, the strength of the porcelain body is not obviously improved, and the bending strength of the MLCC product is not high; when the amount of the additive is too large, the dielectric constant of the dielectric ceramic is slightly lowered, and the temperature stability of the MLCC product is remarkably deteriorated.
When MgO, al 2 O 3 、SiO 2 When the addition amount is small, the product is not sintered compactly, the porcelain body strength is low, and the bending strength of the finished product is poor; al (Al) 2 O 3 And SiO 2 When the amount is too large, spherical BaTiO is caused 3 The sintering process is extremely long and large, the strength of the porcelain body is reduced, and meanwhile, the temperature stability of the product is also deteriorated; when the addition amount of the rare earth additive is small, the core-shell structure is incomplete, and the temperature stability of the product is poor; when the addition amount is too large, baTiO 3 Too many rare earth elements are dissolved in the solution, and the dielectric constant is low; when the amount of the valence-variable element additive is small, the reduction resistance is reduced, and oxygen vacancies are occupiedHigh ratio, poor life; when the addition amount of the valence-variable element additive is too large, the porcelain body is easy to be semi-conductive, and the insulation resistance is low.
In a second aspect, the present invention provides a chip multilayer ceramic capacitor, the dielectric layer of which comprises the dielectric ceramic material.
In a third aspect, the present invention provides a method for manufacturing a chip multilayer ceramic capacitor, comprising the steps of:
(1) Uniformly mixing spherical barium titanate, rod-shaped barium titanate, magnesium oxide, aluminum oxide, silicon oxide, rare earth additives, valence-variable element additives, an organic binder and an organic solvent raw material to obtain ceramic slurry; casting the ceramic slurry into a ceramic film;
(2) Laminating, forming, isostatic pressing and cutting the ceramic film to obtain a laminated green body;
(3) And (3) discharging glue, sintering and covering an external electrode on the green lamination body to obtain the chip type multilayer ceramic capacitor.
As a preferred embodiment of the present invention, in the step (1), the spherical barium titanate has an average particle diameter of 150 to 500nm; the average diameter of the particles of the rod-shaped barium titanate is 0.5-1 mu m, and the length-diameter ratio of the particles of the rod-shaped barium titanate is more than or equal to 2.
Where n is the ratio of the particle length c to the diameter d of the rod-shaped barium titanate (n=c/d).
The inventors of the present invention found that bar-like BaTiO 3 The larger the particle aspect ratio n of (C) is, the more advantageous the rod-like BaTiO is 3 Wherein the two-dimensional orientation arrangement is such that the rod-like barium titanate particles are approximately tiled in the length or width direction of the casting film, and do not take on a vertical state in the thickness direction. Added bar-shaped BaTiO 3 The ceramic material is laid down and tiled under the action of the flow of the casting scraper and the slurry, the two-dimensional planes are arranged in an oriented mode, the liquid phase sintering process is further grown to be longer, the existence of rod-shaped particles is similar to that of a fiber structure, crack propagation can be effectively prevented, the strength of the ceramic body is improved, and therefore the bending strength of an MLCC product is improved.
As a preferred embodiment of the present invention, in the step (1), the film length ratio of the ceramic thin film is equal to or less than 5, wherein the film length ratio is a ratio of the thickness of the ceramic thin film to the particle length of the rod-shaped barium titanate.
The film length ratio k should be less than or equal to 5, wherein the film length ratio k refers to the ratio of the thickness t to the length c of the ceramic thin film, i.e., k=t/c.
Ratio k to rod-like BaTiO 3 The two-dimensional orientation arrangement of (2) plays a key role, and generally the k value ranges from 1 to 5, and the smaller the k value is, the rod-like BaTiO 3 The higher the two-dimensional orientation arrangement degree is; when k > 5, rod-like BaTiO 3 The degree of two-dimensional orientation arrangement of (c) becomes very low.
As a preferred embodiment of the present invention, in the step (1), the viscosity of the ceramic slurry is 50 to 300cps.
When the viscosity of the slurry is too low, the bar-shaped BaTiO which is laid down and tiled is laid down 3 Will move under the inertia effect after casting, resulting in rod-like BaTiO 3 The positions are disordered, and the two-dimensional orientation arrangement degree is low; when the viscosity of the ceramic slurry is too high, on one hand, the casting molding is not facilitated, and on the other hand, the fluidity of the slurry cannot be fully exerted, because some rod-shaped BaTiO which is not contacted with a scraper is not fully utilized 3 The two-dimensional orientation arrangement can be completed through the fluidity of the slurry. Therefore, the viscosity of the ceramic slurry also affects the rod-like BaTiO to some extent 3 When the viscosity of the ceramic slurry is in the above range, the two-dimensional orientation arrangement of the rod-like barium titanate is more preferable.
As a preferred embodiment of the present invention, in the step (1), the casting speed is not less than 20m/s.
As a further preferred embodiment of the present invention, in the step (1), the casting speed is 20 to 90m/s.
Proper casting speed is favorable for fully playing the fluidity of the slurry and improving the rod-shaped BaTiO 3 Is a two-dimensional orientation arrangement degree of the lens.
The thickness, the slurry viscosity and the casting speed are regulated so that the rod-shaped particles are more in a paved state, and the vertical state in the thickness direction is reduced.
As a preferred embodiment of the present invention, in step (1), the organic binder comprises polyvinyl butyral.
In the step (1), the organic solvent comprises at least one of toluene and ethanol as a preferred embodiment of the present invention.
As a preferred embodiment of the present invention, in step (1), the mixing means comprises ball milling.
As a preferred embodiment of the present invention, in step (2), the printing includes screen printing.
In the step (2), the laminate green body is further subjected to a heat treatment at 100 to 300 ℃ for 0.5 to 3 hours as a preferred embodiment of the present invention.
In a preferred embodiment of the present invention, in the step (2), the conductive paste is a conductive paste for internal electrodes containing a base metal material as a main component.
In a preferred embodiment of the present invention, in the step (3), the sintering is performed at a sintering temperature of 1100 to 1300 ℃ at a heating rate of 3 to 20 ℃/min for 1 to 2 hours.
In the step (3), the sintering atmosphere is a reducing atmosphere comprising H 2 、N 2 、H 2 And a reducing atmosphere composed of O gas.
The heating rate, sintering temperature and sintering heat preservation time all influence the growth degree of the crystal grains, and the size of the crystal grains can influence the strength of the ceramic. The slower the temperature rising rate, the higher the sintering temperature, the longer the sintering heat preservation time, the more easily the grains grow up, and the more compact the ceramic body is sintered, but the higher the sintering temperature or the longer the sintering heat preservation time, the abnormally grown grains, and the lower the ceramic strength.
In a preferred embodiment of the present invention, in step (3), at least one of the external electrode Cu electrode and Ag electrode is formed.
The preparation method of the multilayer ceramic capacitor is similar to the dielectric ceramic material, and the difference is that the preparation method of the multilayer ceramic capacitor further comprises the steps of printing conductive paste on the surface of the ceramic film to form a conductive pattern and covering the laminated green body with an external electrode after glue discharging and sintering.
Compared with the prior art, the invention has the following beneficial effects: the invention increases the intensity of the ceramic medium by introducing the rod-shaped barium titanate particles, and ensures that the MLCC product has good mechanical property, electrical property and temperature stability by regulating and controlling the content and length-diameter ratio of the constituent components, the rheological property of slurry, the casting process and the sintering process.
Drawings
FIG. 1 is a schematic diagram showing a mechanical property test of a multilayer ceramic capacitor.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described by means of specific examples.
The raw materials used in the following examples, including spherical barium titanate of different types, rod-shaped barium titanate, and the like, are commercially available or self-made, unless otherwise specified. Such as spherical BaTiO as the main component material 3 Can be BaTiO prepared by a solid phase method 3 Powder, but not limited to BaTiO prepared by solid phase method 3 BaTiO prepared by hydrothermal method, coprecipitation method, oxalate method and the like 3 All can be used; in addition, rod-shaped barium titanate BT (L) may be BaTiO prepared by molten salt method 3 The rod-like powder may be BaTiO prepared by a method such as eutectic solidification 3 A rod-shaped powder.
Example 1
The dielectric ceramic material can be represented by the general formula (1-1):
BaTiO 3 (S)+a BaTiO 3 (L)+b MgO+c Al 2 O 3 +d SiO 2 + e M1+ f M2 (formula 1-1), wherein M1 is rare earth additive La 2 O 3 M2 is a valence-variable element additive MnO 2 。
Spherical BaTiO in this example 3 (S) an average particle diameter of 200nm; rod-shaped BaTiO 3 The particle diameter d of (L) is 0.5-0.6 μm, and the aspect ratio n (n=c/d) is 5; wherein a=25 mol%, b=0.3 mol%, c=1 mol%, d=2.5 mol%, e=1.5 mol%, f=0.2 mol%, and the rest of the components are spherical BaTiO 3 。
The preparation method of the multilayer ceramic capacitor containing the dielectric ceramic material of the embodiment comprises the following steps:
(1) Sintering auxiliary agent MgO and Al according to a preset proportion 2 O 3 、SiO 2 、La 2 O 3 And MnO 2 Is composed of BaTiO as main component 3 Adding the ceramic slurry and an organic binder (polyvinyl butyral), an organic solvent (toluene) and a ball milling medium (zirconia balls) into a ball mill, and carrying out wet mixing and dispersion to prepare uniform ceramic slurry, wherein the viscosity of the slurry is controlled at 50cps;
(2) Then, the bar-shaped BaTiO is prepared 3 Adding into ceramic slurry, stirring at high speed, and casting into thin film (film thickness 5-6 μm) with doctor blade method at 20m/s, wherein the rod-like BaTiO is prepared 3 The ratio k of the length c to the film thickness t (i.e., k=t/c) is 2;
(3) Next, a conductive paste for internal electrodes containing a Ni base metal material as a main component is prepared, and a specific conductive film pattern is formed on the surface of the molded film by screen printing; then, the film of the printed electrode is laminated and formed according to a given dislocation mode and requirements, isostatic pressing is carried out, and the film is cut into green bodies with given sizes;
(4) Then, the green body is heat treated in air (250 ℃ for 2 hours) to remove organic matters in the green body; then, at the same time, by H 2 -N 2 -H 2 Sintering is carried out for 2 hours at the sintering temperature of 1100 ℃ under the strong reducing atmosphere composed of O gas, and the heating rate is 15 ℃/min, so that the dielectric ceramic body is prepared.
(5) Finally, external electrodes (Ag) are covered on both ends of the dielectric ceramic body to manufacture a chip-type multilayer ceramic capacitor.
Examples 2 to 4
Examples 2 to 4 differ from example 1 only in the rod-like BaTiO 3 The adding amount of (2) is different, specifically:
example 2: wherein a=5 mol%, b=0.3 mol%, c=1 mol%, d=2.5 mol%, e=1.5 mol%, f=0.2 mol%, and the rest is spherical BaTiO 3 ；
Example 3: wherein a=15 mol%, b=0.3 mol%, c=1 mol%, d=2.5 mol%, e=1.5 mol%, f=0.2 mol%, and the rest is spherical BaTiO 3 ；
Example 4: wherein a=35 mol%, b=0.3 mol%, c=1 mol%, d=2.5 mol%, e=1.5 mol%, f=0.2 mol%, and the rest component is spherical BaTiO 3 。
Examples 5 to 9
Examples 5 to 9 differ from example 1 only in the rod-like BaTiO 3 Aspect ratio and/or film thickness t with rod-like BaTiO 3 The ratio k of the particle lengths c of (c) is different, specifically:
example 5: rod-shaped BaTiO 3 Aspect ratio n=2, film thickness t and rod-like BaTiO 3 The ratio k=3 of the length c of (a);
example 6: rod-shaped BaTiO 3 Aspect ratio n=3, film thickness t and rod-like BaTiO 3 The ratio k=2 of the length c of (a);
example 7: rod-shaped BaTiO 3 Aspect ratio n=8, film thickness t and rod-like BaTiO 3 The ratio k=3 of the length c of (a);
example 8: rod-shaped BaTiO 3 Aspect ratio n=5, film thickness t and rod-like BaTiO 3 The ratio k=2 of the length c of (a);
example 9: rod-shaped BaTiO 3 Aspect ratio n=6, film thickness t and rod-like BaTiO 3 The ratio k=5 of the length c of (c).
TABLE 1 rod-shaped BaTiO of example 1, examples 5-9 and comparative examples 4-5 3 Related parameters
Figure BDA0004198198360000071
Examples 10 to 14
Examples 10 to 14 differ from example 1 only in the content of sintering aids, specifically:
example 10: a=25 mol%, b=0.1 mol%, c=0.5 mol%, d=5 mol%, e=4.5 mol%, f=0.05 mol%, and the rest in the formula (1-1)The component is spherical BaTiO 3 ；
Example 11: a=25 mol%, b=2 mol%, c=1 mol%, d=3.5 mol%, e=3 mol%, f=0.5 mol% in the formula (1-1), and the rest components are spherical BaTiO 3 ；
Example 12: a=25 mol%, b=3 mol%, c=1.5 mol%, d=2 mol%, e=0.5 mol%, f=0.35 mol%, and the rest is spherical BaTiO in the formula (1-1) 3 ；
Example 13: a=25 mol%, b=5 mol%, c=2 mol%, d=1 mol%, e=2 mol%, f=0.15 mol% in the formula (1-1), and the rest components are spherical BaTiO 3 。
Example 14: a=25 mol%, b=0.3 mol%, c=1 mol%, d=2.5 mol%, e=1.5 mol%, f=0.6 mol%, in the formula (1-1), the rest is spherical BaTiO 3 ；
Examples 15 to 17
Examples 15 to 17 differ from example 1 only in the slurry viscosity and the casting speed, specifically:
example 15: the casting speed is 30m/s, and the viscosity of the slurry is controlled to be 250cps;
example 16: the casting speed is 60m/s, and the viscosity of the slurry is controlled to be 150cps;
example 17: the casting speed was 90m/s, and the slurry viscosity was controlled to 100cps.
Examples 18 to 20
Examples 18 to 20 differ from example 1 only in the sintering process parameters, specifically:
example 18: heating to 1300 ℃ at a heating rate of 3 ℃/min, and sintering for 2 hours;
example 19: heating to 1250 ℃ at a heating rate of 10 ℃/min, and sintering for 1.5 h;
example 20: the temperature was raised to 1200℃at a heating rate of 20℃per minute, and sintering was performed for 1 hour.
Comparative examples 1 to 3
Comparative examples 1 to 3 differ from example 1 only in the rod-like BaTiO 3 The adding amount of (2) is different, specifically:
comparisonExample 1: wherein a=0, b=0.3 mol%, c=1 mol%, d=2.5 mol%, e=1.5 mol%, f=0.2 mol%, and the remaining components are spherical BaTiO 3 ；
Comparative example 2: wherein a=2 mol%, b=0.3 mol%, c=1 mol%, d=2.5 mol%, e=1.5 mol%, f=0.2 mol%, and the rest component is spherical BaTiO 3 ；
Comparative example 3: wherein a=40 mol%, b=0.3 mol%, c=1 mol%, d=2.5 mol%, e=1.5 mol%, f=0.2 mol%, and the rest is spherical BaTiO 3 。
Comparative examples 4 to 5
Comparative examples 4 to 5 differ from example 1 only in the rod-like BaTiO 3 Aspect ratio of (c) or rod-like BaTiO 3 The ratio k of the length c to the film thickness t is different, specifically:
comparative example 4: the rod-shaped BaTiO 3 N is equal to 1;
comparative example 5: the casting film thickness t and the rod-shaped BaTiO 3 The ratio k of the lengths c of (2) is equal to 10.
Comparative examples 6 to 10
Comparative examples 6 to 10 differ from example 1 only in the component content of the sintering aid, specifically:
comparative example 6: a=25 mol%, b=6 mol%, c=3 mol%, d=6 mol%, e=1.5 mol%, f=0.2 mol% in the formula (1-1), and the rest components are spherical BaTiO 3 ；
Comparative example 7: a=25 mol%, b=0.01 mol%, c=0.05 mol%, d=0.1 mol%, e=1.5 mol%, f=0.2 mol%, and the rest of the components are spherical BaTiO in the formula (1-1) 3 ；
Comparative example 8: a=25 mol%, b=0.3 mol%, c=1 mol%, d=2.5 mol%, e=5 mol%, f=0.2 mol% in the formula (1-1), and the rest is spherical BaTiO 3 ；
Comparative example 9: a=25 mol%, b=0.3 mol%, c=1 mol%, d=2.5 mol%, e=0.1 mol%, f=0.2 mol%, in the formula (1-1), the rest is spherical BaTiO 3 ；
Comparative example 10: a=25 mol%, b=0.3 mol%, c=1 mol%, d in the formula (1-1)=2.5 mol%, e=1.5 mol%, f=0.01 mol%, and the rest is spherical BaTiO 3 。
Comparative examples 11 to 13
Comparative examples 11 to 13 differ from example 1 only in the slurry viscosity and the casting speed, specifically:
comparative example 11: the casting speed is 10m/s;
comparative example 12: the viscosity of the slurry is controlled to be 80cps;
comparative example 13: the slurry viscosity was controlled to 350cps.
Comparative examples 14 to 19
Comparative examples 14 to 19 differ from example 1 only in the sintering process parameters, specifically:
comparative example 14: heating to 1300 ℃ at a heating rate of 25 ℃/min, and sintering for 2 hours;
comparative example 15: heating to 1300 ℃ at a heating rate of 1 ℃/min, and sintering for 2 hours;
comparative example 16: heating to 1350 ℃ at a heating rate of 20 ℃/min, and sintering for 2 hours;
comparative example 17: heating to 1000 ℃ at a heating rate of 20 ℃/min, and sintering for 2 hours;
comparative example 18: heating to 1300 ℃ at a heating rate of 20 ℃/min, and sintering for 3 hours;
comparative example 19: the temperature is raised to 1300 ℃ at a heating rate of 20 ℃/min, and sintering is carried out for 0.5 h.
Performance test of multilayer ceramic capacitor
(1) And (3) electrical property detection:
table 2 test items
Figure BDA0004198198360000091
Figure BDA0004198198360000101
(2) And (3) mechanical property detection:
the invention adopts a limit test to detect the strength of a sample, the test substrate is a PCB board, and the test substrate is applied at a speed of 0.5mm/s with a force of 5N, so that the bending depth is l2mm, and the application time is 10s, as shown in figure 1. No visual damage should be observed after the test, the change of capacitor capacity after the test is in the range of 4-10%, the number of the samples in each group is 12, and the samples are judged to be qualified if the measured samples meet the requirement.
TABLE 3 results of dielectric ceramic body properties prepared in examples and comparative examples
Figure BDA0004198198360000102
Figure BDA0004198198360000111
As can be seen from examples 1 to 20, the dielectric ceramic material prepared by the invention has good mechanical property, electrical property and temperature characteristic, wherein the dielectric constant range is 2512 to 4022, the TCC meets X7R standard, and the capacity change is 4 to 10%.
As is clear from example 1 and comparative examples 1 to 3, if no bar-like BaTiO is added 3 Or the addition amount is too small, and the mechanical property of the dielectric ceramic material is poor; rod-like BaTiO 3 If the amount of the additive is too large, the strength can be improved, but the dielectric constant of the dielectric ceramic is slightly lowered, and the temperature stability of the product is remarkably deteriorated.
As is clear from examples 1 and comparative examples 4 to 5, the dielectric ceramic material has poor mechanical properties because of too small aspect ratio or too large film length ratio.
As can be seen from example 1 and comparative examples 6 to 10, if the sintering aid is added too much, spherical BaTiO results 3 The grains are abnormally grown, and the strength of the porcelain body is reduced; if the addition of the sintering aid is too small, the product is not sintered compactly enough, and the strength of the porcelain body is low. Wherein, if rare earth additive is added too little, the core-shell structure is incomplete, the temperature stability of the product is poor, and when the rare earth additive is added too much, baTiO is used 3 Too much rare earth element in solid solution and dielectric constantLower than the former; when the number of the valence-variable element additives is small, the anti-reduction characteristic is reduced, the oxygen vacancy ratio is high, and the service life is poor; when the addition amount of the valence-variable element additive is too large, the porcelain body is easy to be semi-conductive, and the insulation resistance is low.
As can be seen from examples 1 and comparative examples 11 to 13, if the casting speed is too low or the viscosity of the slurry is too low, the fluidity of the slurry is not easily exerted, the two-dimensional orientation arrangement degree of the rod-like particles is low, and the strength of the product is not improved perfectly; if the viscosity of the slurry is too high, the casting molding is not facilitated, and the strength of the product is difficult to improve.
As can be seen from examples 1 and comparative examples 14 to 19, the temperature rise rate during sintering is too high, the heat preservation time is too long, and the sintering temperature is too high, which can cause abnormal growth of crystal grains and lower ceramic strength; the heat preservation time is too short, the sintering temperature is too low, the sintering densification is not facilitated, and the ceramic strength is also low.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

1. A dielectric ceramic material comprising the following components in mole percent: 5-35% of rod-shaped barium titanate, 0.1-5% of magnesium oxide, 0.1-2% of aluminum oxide, 1-5% of silicon oxide, 0.5-4.5% of rare earth additive, 0.05-0.6% of valence-changing element additive and the balance of spherical barium titanate;
the rare earth elements in the rare earth additive comprise at least one of Dy, ho, Y, yb, la, ce, er, gd; the valence-changing element in the valence-changing element additive comprises at least one of Mn, V, cr, mo.
2. The dielectric ceramic material of claim 1, wherein the dielectric ceramic material comprises the following components in mole percent: 5-35% of rod-shaped barium titanate, 0.3-3% of magnesium oxide, 0.5-1.5% of aluminum oxide, 2-3.5% of silicon oxide, 1-2% of rare earth additive, 0.1-0.3% of valence-changing element additive and the balance of spherical barium titanate.
3. A chip multilayer ceramic capacitor, characterized in that the dielectric layer thereof comprises the dielectric ceramic material according to claim 1 or 2.
4. A method for manufacturing a chip multi-layer ceramic capacitor as claimed in claim 3, comprising the steps of:
(1) Uniformly mixing spherical barium titanate, rod-shaped barium titanate, magnesium oxide, aluminum oxide, silicon oxide, rare earth additives, valence-variable element additives, an organic binder and an organic solvent raw material to obtain ceramic slurry; casting the ceramic slurry into a ceramic film;
(2) Printing conductive paste on the surface of the ceramic film to form a conductive pattern, and performing lamination forming, isostatic pressing and cutting on the ceramic film with the conductive pattern to obtain a laminated green body;
(3) And (3) discharging glue and sintering the laminated green body, and covering an external electrode to obtain the multilayer ceramic capacitor.
5. The method for producing a chip multi-layer ceramic capacitor according to claim 4, wherein in said step (1), said spherical barium titanate has an average particle diameter of 150 to 500nm; the average diameter of the particles of the rod-shaped barium titanate is 0.5-1 mu m, and the length-diameter ratio of the particles of the rod-shaped barium titanate is more than or equal to 2.
6. The method of producing a chip multi-layer ceramic capacitor according to claim 4, wherein in the step (1), a film length ratio of the ceramic thin film is equal to or less than 5, wherein the film length ratio is a ratio of a thickness of the ceramic thin film to a particle length of the rod-like barium titanate.
7. The method for manufacturing a chip multi-layer ceramic capacitor as set forth in claim 4, wherein in said step (1), the viscosity of said ceramic paste is 50 to 300cps.
8. The method for producing a chip multilayer ceramic capacitor according to claim 4, wherein in the step (1), the casting speed is not less than 20m/s; in the step (3), the sintering is performed for 1-2 hours at the sintering temperature of 1100-1300 ℃ at the heating rate of 3-20 ℃/min.
9. The method for manufacturing a chip multi-layer ceramic capacitor as defined in claim 4, wherein in said step (1), said organic binder comprises polyvinyl butyral; in the step (1), the organic solvent comprises at least one of toluene and ethanol; in step (1), the mixing mode comprises ball milling.
10. The method for manufacturing a chip multi-layer ceramic capacitor as set forth in claim 4, wherein in the step (2), the printing includes screen printing; in the step (2), the laminated green body is further subjected to heat treatment, wherein the heat treatment is carried out for 0.5-3 hours at 100-300 ℃; in the step (2), the conductive paste is a conductive paste for internal electrodes containing a base metal material as a main component.
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