CN109231977B - High-temperature stable dielectric ceramic material and preparation method thereof - Google Patents

High-temperature stable dielectric ceramic material and preparation method thereof Download PDF

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CN109231977B
CN109231977B CN201811300433.3A CN201811300433A CN109231977B CN 109231977 B CN109231977 B CN 109231977B CN 201811300433 A CN201811300433 A CN 201811300433A CN 109231977 B CN109231977 B CN 109231977B
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刘志甫
彭笑笑
李永祥
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to aThe high-temperature stable medium ceramic material has a sphene structure and a chemical formula of the composition of the sphene structure is CaTi1‑xM10.5xM20.5xSiO5Wherein M1 and M2 are metal ions, x is more than 0 and less than or equal to 10 percent, and x is more than or equal to 3 and less than or equal to 5 percent.

Description

High-temperature stable dielectric ceramic material and preparation method thereof
Technical Field
The invention relates to a high-temperature stable dielectric ceramic material and a preparation method thereof, in particular to a high-temperature stable sphene-structure multilayer ceramic capacitor dielectric ceramic material and a preparation method thereof, and belongs to the technical field of functional ceramic materials.
Background
A Multilayer Ceramic Capacitor (MLCC) is used as an important element for blocking, coupling, bypassing, filtering, tuning a loop, and the like, and is widely applied to various fields such as consumer electronics, wireless communication, automotive electronics, and weaponry. Particularly, the fields of aerospace, oil drilling and the like require that an electronic system can normally and stably work in an extremely harsh environment, which requires that the MLCC can work at a high temperature of 200 ℃ or above. Therefore, it is important to search for a ceramic dielectric material having high dielectric temperature stability.
The most studied dielectric materials for high temperature capacitors are based on a composite of two or more ferroelectrics or relaxor ferroelectrics. For ferroelectric or relaxor ferroelectric ceramics applied to 200 ℃ or above, the perovskite structure high dielectric constant material is taken as a main characteristic, although the use condition at the temperature of 200 ℃ can be met, after the temperature exceeds the Curie temperature of one material in a composite medium, the dielectric constant can obviously fluctuate along with the temperature rise and fall due to the Curie-Weiss effect, and the long-term stability of the material at the high temperature is greatly influenced.
The dielectric constant of a linear medium is generally unaffected by an applied electric field. Therefore, although linear dielectrics generally have a relatively low dielectric constant, high energy density can be achieved due to their high dielectric breakdown strength and large band gap. Therefore, if a linear dielectric can have good high-temperature stability, a capacitor dielectric material having high energy storage density and excellent performance that can operate at high temperatures is expected.
The literature reports that sphene structural material Ca (Ti)0.85Zr0.15)SiO5(Applied Physics Letters, 108, 062902, 2016) has excellent dielectric temperature stability and electrical insulation characteristics between 300-780K, a relative dielectric constant of about 43 in the temperature range, a dielectric loss of less than 0.05, and a material resistance of more than 10 below 523K11Omega cm, but sphene structural material Ca (Ti)0.85Zr0.15)SiO5The relative dielectric constant of (2) is low.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a capacitor dielectric material with high temperature stability and a preparation method thereof.
In one aspect, the invention provides a high-temperature stable dielectric ceramic material, which has a sphene structure and a chemical formula of the composition of the sphene structure1-xM10.5xM20.5xSiO5Wherein M1 and M2 are metal ions, and x is more than 0 and less than or equal to 10 percent.
The invention obtains relatively high dielectric constant by the electrovalence co-doping of the sphene structural ceramic and the like, and has smaller dielectric loss and high insulation resistance. By doping M1 and M2 with different ionic radii from Ti ions, the valence can be effectively balanced and the lattice can be twisted. The invention also improves the grain size by sanding and other modes, obtains larger breakdown strength and further obtains better energy storage density. In addition, the trivalent M1 and the pentavalent M2 of Ti sites are doped in equal quantity, so that isovalent co-doping is realized, the generation of the anti-ferroelectric phase of the sphene structure is avoided, and the dielectric temperature stability of the dielectric material is improved.
Preferably, two metal ions M1 and M2 are used to replace the Ti ion together, and the sum of the average valence of the two metal ions M1 and M2 is + 4.
Preferably, M1 is at least one of metal elements In the three groups of Al, Ga and In, and M2 is at least one of Nb and Ta. The invention can effectively balance the electrovalence and make the crystal lattice generate torsion by doping the trivalent M1 and the pentavalent M2 with the same amount and the ionic radius different from that of the Ti ions. In addition, the addition of the doping element (M1 is one of Al, Ga and In, M2 is one of Nb and Ta) can also inhibit the intrinsic phase transformation of the sphene structural material, so that the stable dielectric property can be obtained within the range of room temperature to 300 ℃.
Preferably, the dielectric constant of the high-temperature stable dielectric ceramic material is 38-57, preferably 47-53 at 25-300 ℃.
Preferably, the high-temperature stable medium ceramic material has a compressive strength of more than 900kV/cm, preferably more than 1000 kV/cm.
On the other hand, the invention also provides a preparation method of the high-temperature stable dielectric ceramic material, which comprises the following steps:
weighing Ca source, Si source, Ti source, M1 source and M2 source powder according to the composition chemical formula of the high-temperature stable medium ceramic material, and mixing to obtain mixed powder;
pre-burning the obtained mixed powder at 800-1200 ℃ to obtain pre-burned powder;
pressing and molding the obtained pre-sintered powder and a binder to obtain a blank;
and (3) removing the glue from the obtained blank, and sintering at 1250-1350 ℃ for 2-6 hours to obtain the high-temperature stable medium ceramic material.
Preferably, the Ca source is CaCO3The Si source is SiO2The Ti source is TiO2The M1 source is an oxide of M1 and the M2 source is an oxide of M2.
Preferably, the burn-in protocol comprises: firstly, preserving heat for 1-4 hours at 800-1000 ℃, and then preserving heat for 4-8 hours at 1100-1200 ℃; preferably, the temperature is first maintained at 900 ℃ for 2 hours, and then raised to 1150 ℃ for 6 hours. According to the invention, the high-temperature stable dielectric ceramic material has wide temperature stability and high pressure-resistant strength by isovalent codoping of two elements and two-step presintering in the preparation process.
Preferably, the temperature rise rate of the pre-sintering is 2-5 ℃/min.
Preferably, the binder is at least one of polyvinyl alcohol (PVA) and polyvinyl butyral (PVB); the addition amount of the binder is 6-8 wt% of the mass of the pre-sintered powder.
Preferably, the compression molding mode is dry compression molding and/or isostatic pressing, and preferably, dry compression molding is firstly carried out, and then isostatic pressing is carried out; the pressure of the dry pressing is 0.5-2 MPa, and the pressure of the isostatic pressing is 200-300 MPa.
Preferably, the temperature of the rubber discharge is 450-650 ℃, and the time is 0.5-2 hours.
Preferably, the heating rate of the binder removal is 2-5 ℃/min; the temperature rise rate of the sintering is 3-5 ℃/min.
The invention has the beneficial effects that: by adjusting the proportion of Ti/(M1-M2), the pure-phase (M1-M2) codoped sphene structural ceramic is prepared, and a better temperature coefficient of capacitance is obtained within the temperature range of 25 ℃ to 300 ℃. At room temperature, the high breakdown strength and energy storage density can be obtained, and the good energy storage efficiency can be ensured within the temperature range of 25-180 ℃.
Drawings
FIG. 1 is an XRD pattern of the high temperature stable dielectric ceramic materials prepared in examples 1-4 and comparative example 1 at room temperature, and it can be seen that pure CaTiSiO is formed in all the examples and comparative examples5Phase, but when x is 0 and x is 0.5%, appears in the antiferroelectric CaTiSiO5 phase
Figure BDA0001852226890000031
And
Figure BDA0001852226890000032
the characteristic peaks and the rest characteristic peaks are paraelectric phases.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the invention, the structure of the sphene is CaTiSiO5The material Ti potential isoelectric co-doping improves the dielectric constant and keeps other performances on the basis of balancing valence, thereby obtaining high energy storage densityDegree and capacitor capacitance density. Wherein the high-temperature stable medium ceramic material can have a chemical formula of CaTi1-xM10.5xM20.5xSiO5Wherein M1 is one of Al, Ga and In, M2 is one of Nb and Ta, and x is more than 0 and less than or equal to 10 percent. When the value of x exceeds 10 percent, the defects of the obtained material are increased, the dielectric constant of the material is obviously reduced, and the compressive strength of the material is greatly reduced. More preferably, x is 3% to 5%.
In an optional embodiment, the high-temperature stable dielectric ceramic material has a dielectric constant of 47-57 at 25-300 ℃.
In one embodiment of the invention, the high temperature stable dielectric ceramic material is prepared by a solid phase reaction method. The preparation method of the high temperature stable dielectric ceramic material is exemplarily described as follows.
According to a molar ratio of 1: 1: (1-x): 0.5 x: the Ca source, Si source, Ti source, Al source, and Nb source were weighed at 0.5x and mixed to obtain a mixed powder. Wherein the Ca source is CaCO3. The Si source may be SiO2. The Ti source may be TiO2. The M1 source can be an oxide of M1 (e.g., Al)2O3、Ga2O3、In2O3). The M2 source is an oxide of M2 (e.g., Nb)2O3、Ta2O3). The mixing may be by ball milling. Preferably, the mixed powder is obtained by performing drying treatment and sieving after ball milling and mixing. As an example, CaCO is weighed in terms of molar ratio3、SiO2、TiO2、Al2O3、Nb2O5Preparing a mixture by taking the powder as a raw material, adding a ball milling auxiliary agent into the mixture, fully ball-milling, drying, fully grinding the dried mixture, and sieving with a 60-mesh sieve to obtain mixed powder.
The mixed powder is subjected to a pre-firing treatment at 900 ℃ or higher (for example, 900 to 1150 ℃). Preferably, twice presintering is adopted, heat preservation is carried out for 2-4 hours at 900-1000 ℃, presintering powder with pure phases is obtained for full heat absorption of the powder, and heat preservation is carried out for 4-7 hours at 1100-1150 ℃, so that presintering powder with pure sphene structural phases is obtained. More preferably, the temperature is first maintained at 900 ℃ for 2 hours, and then the temperature is raised to 1150 ℃ and maintained for 6 hours. Wherein the temperature rise rate of the pre-sintering can be 2-5 ℃/min. In addition, the presintering powder is dried and sieved after being ball-milled, and then the presintering powder is treated at 760 ℃ to remove redundant organic matters.
And mixing and granulating the pre-sintered powder and the binder, sieving, and performing compression molding to obtain a blank.
And (3) after removing the glue, sintering the blank at 1250-1300 ℃ for 2-6 hours to obtain the high-temperature stable medium ceramic material. Wherein the temperature of the binder removal can be 450-650 ℃, and the time is 0.5-2 hours. The heating rate of the binder removal can be 2-5 ℃/min. The temperature rise rate of the sintering can be 3-5 ℃/min.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Selecting Ti: al: the Nb molar ratio is 1: 0: 0, mixing CaCO3、SiO2、TiO2、Al2O3And Nb2O5The powder is in accordance with CaTiSiO5Mixing the molecular formula after weighing, ball-milling for 6 hours, and drying to obtain mixed powder;
continuously grinding the mixed powder, sieving, keeping the temperature of the sieved mixed powder (mixed powder) at 900 ℃ for 2 hours, and then heating to 1150 ℃ and keeping the temperature for 6 hours;
the pre-fired powder (pre-fired powder) was ball milled again in a nylon jar for 6 hours and then dried. Grinding and sieving the dried powder, and then placing the powder into a furnace to be treated for 30 minutes at 760 ℃, thereby removing organic matters in the powder;
the above powder was sanded with alcohol at a rate of 2000 rpm for 1 hour. And drying the mixed solution after sanding, adding 8 wt% of PVA as a binder, fully and uniformly grinding, and sieving. Sieving, and pressing into sheet with diameter of about 13 mm. Sealing the pressed sheet, and performing isostatic pressing in transformer oil at a pressure of 250 MPa;
and (3) putting the pressed slices into a furnace, heating to 600 ℃ at the rate of 3 ℃ per minute, preserving the heat for 2 hours, and removing the glue. Then the temperature is raised to 1250 ℃ at the rate of 5 ℃ per minute, and the sintering is carried out after the temperature is kept for 6 hours. The XRD of the resulting sample is shown in FIG. 1.
Example 2
Selecting Ti: al: nb molar ratio 0.995: 0.0025: 0.0025, adding CaCO3、SiO2、TiO2、Al2O3And Nb2O5The powder is in accordance with CaTi0.995Al0.0025Nb0.0025SiO5Mixing the molecular formula after weighing, ball-milling for 6 hours, and drying to obtain mixed powder;
continuously grinding the mixed powder, sieving, keeping the temperature of the sieved mixed powder (mixed powder) at 900 ℃ for 2 hours, and then heating to 1150 ℃ and keeping the temperature for 6 hours;
the pre-fired powder (pre-fired powder) was ball milled again in a nylon jar for 6 hours and then dried. Grinding and sieving the dried powder, and then placing the powder into a furnace to be treated for 30 minutes at 760 ℃, thereby removing organic matters in the powder;
the above powder was sanded with alcohol at a rate of 2000 rpm for 1 hour. And drying the mixed solution after sanding, adding 8 wt% of PVA as a binder, fully and uniformly grinding, and sieving. Sieving, and pressing into sheet with diameter of about 13 mm. Sealing the pressed sheet, and performing isostatic pressing in transformer oil at a pressure of 250 MPa;
and (3) putting the pressed slices into a furnace, heating to 600 ℃ at the rate of 3 ℃ per minute, preserving the heat for 2 hours, and removing the glue. Then, the temperature is raised to 1270 ℃ at the rate of 5 ℃ per minute, and the temperature is kept for 6 hours for sintering. The XRD of the resulting sample is shown in FIG. 1.
Example 3
Selecting Ti: al: nb molar ratio of 0.97: 0.015: 0.015, mixing CaCO3、SiO2、TiO2、Al2O3And Nb2O5The powder is in accordance with CaTi0.97Al0.015Nb0.015SiO5Weighing molecular formulas, mixing, using absolute ethyl alcohol as a medium and zirconium dioxide balls as a grinding medium, ball-grinding in a nylon tank for 6 hours, and drying to obtain mixed powder;
continuously grinding the mixed powder, sieving, keeping the temperature of the sieved mixed powder (mixed powder) at 900 ℃ for 2 hours, and then heating to 1150 ℃ and keeping the temperature for 6 hours;
the pre-fired powder (pre-fired powder) was ball milled again in a nylon jar for 6 hours and then dried. Grinding and sieving the dried powder, and then placing the powder into a furnace to be treated for 30 minutes at 760 ℃, thereby removing organic matters in the powder;
the above powder was sanded with alcohol at a rate of 2000 rpm for 1 hour. And drying the mixed solution after sanding, adding 8 wt% of PVA as a binder, fully and uniformly grinding, and sieving. Sieving, and pressing into sheet with diameter of about 13 mm. Sealing the pressed sheet, and performing isostatic pressing in transformer oil at a pressure of 250 MPa;
and (3) putting the pressed slices into a furnace, heating to 600 ℃ at the rate of 3 ℃ per minute, preserving the heat for 2 hours, and removing the glue. Then, the temperature is raised to 1270 ℃ at the rate of 5 ℃ per minute, and the temperature is kept for 6 hours for sintering. The XRD of the resulting sample is shown in FIG. 1.
Example 4
Selecting Ti: al: nb molar ratio is 0.95: 0.025: 0.025, mixing with CaCO3、SiO2、TiO2、Al2O3And Nb2O5The powder is in accordance with CaTi0.95Al0.025Nb0.025SiO5Weighing molecular formulas, mixing, using absolute ethyl alcohol as a medium and zirconium dioxide balls as a grinding medium, ball-grinding in a nylon tank for 6 hours, and drying to obtain mixed powder;
continuously grinding the mixed powder, sieving, keeping the temperature of the sieved mixed powder (mixed powder) at 900 ℃ for 2 hours, and then heating to 1150 ℃ and keeping the temperature for 6 hours;
the pre-fired powder (pre-fired powder) was ball milled again in a nylon jar for 6 hours and then dried. Grinding and sieving the dried powder, and then placing the powder into a furnace to be treated for 30 minutes at 760 ℃, thereby removing organic matters in the powder;
the above powder was sanded with alcohol at a rate of 2000 rpm for 1 hour. And drying the mixed solution after sanding, adding 8 wt% of PVA as a binder, fully and uniformly grinding, and sieving. Sieving, and pressing into sheet with diameter of about 13 mm. Sealing the pressed sheet, and performing isostatic pressing in transformer oil at a pressure of 250 MPa;
and (3) putting the pressed slices into a furnace, heating to 600 ℃ at the rate of 3 ℃ per minute, preserving the heat for 2 hours, and removing the glue. Then, the temperature is raised to 1270 ℃ at the rate of 5 ℃ per minute, and the temperature is kept for 6 hours for sintering. The XRD of the resulting sample is shown in FIG. 1.
Comparative example 1
Selecting Ti: al: nb molar ratio is 0.8: 0.1: 0.1, mixing CaCO3、SiO2、TiO2、Al2O3And Nb2O5The powder is in accordance with CaTi0.8Al0.1Nb0.1SiO5Weighing molecular formulas, mixing, using absolute ethyl alcohol as a medium and zirconium dioxide balls as a grinding medium, ball-grinding in a nylon tank for 6 hours, and drying to obtain mixed powder;
continuously grinding the mixed powder, sieving, keeping the temperature of the sieved mixed powder (mixed powder) at 900 ℃ for 2 hours, and then heating to 1150 ℃ and keeping the temperature for 6 hours;
the pre-fired powder (pre-fired powder) was ball milled again in a nylon jar for 6 hours and then dried. Grinding and sieving the dried powder, and then placing the powder into a furnace to be treated for 30 minutes at 760 ℃, thereby removing organic matters in the powder;
the above powder was sanded with alcohol at a rate of 2000 rpm for 1 hour. And drying the mixed solution after sanding, adding 8 wt% of PVA as a binder, fully and uniformly grinding, and sieving. Sieving, and pressing into sheet with diameter of about 13 mm. Sealing the pressed sheet, and performing isostatic pressing in transformer oil at a pressure of 250 MPa;
and (3) putting the pressed slices into a furnace, heating to 600 ℃ at the rate of 3 ℃ per minute, preserving the heat for 2 hours, and removing the glue. Then the temperature is raised to 1250 ℃ at the rate of 5 ℃ per minute, and the sintering is carried out after the temperature is kept for 6 hours.
Example 5
Silver electrodes were printed on both surfaces of the high temperature stable dielectric ceramic materials prepared in examples 1 to 4 and comparative example 1, and the dielectric constant, dielectric strength and insulation resistance were measured after sintering, and the obtained data are shown in table 1.
Table 1 shows the electrical property parameters of the high-temperature stable dielectric ceramic materials prepared in examples 1-4 of the present invention and comparative example 1:
Figure BDA0001852226890000061
Figure BDA0001852226890000071

Claims (10)

1. the high-temperature stable dielectric ceramic material is characterized by having a sphene structure and having a chemical formula of CaTi1-xM10.5xM20.5xSiO5Wherein M1 is Al, M2 is Nb, and x is more than or equal to 3 and less than or equal to 5 percent.
2. The high temperature stable dielectric ceramic material of claim 1 wherein Ti ions are replaced by two metal ions M1 and M2 together, and the sum of the average valence of the two metal ions M1 and M2 is + 4.
3. The high temperature stable dielectric ceramic material of claim 1, wherein the dielectric constant of the high temperature stable dielectric ceramic material is 38-57 at 25-300 ℃.
4. The high temperature stable dielectric ceramic material of claim 3, wherein the dielectric constant of the high temperature stable dielectric ceramic material is 47-53 at 25-300 ℃.
5. The high temperature stable dielectric ceramic material of claim 1 having a compressive strength greater than 900 kV/cm.
6. The high temperature stable dielectric ceramic material of claim 5 having a compressive strength greater than 1000 kV/cm.
7. A method of making a high temperature stable dielectric ceramic material as claimed in any one of claims 1 to 6, comprising:
weighing Ca source, Si source, Ti source, M1 source and M2 source powder according to the composition chemical formula of the high-temperature stable medium ceramic material, and mixing to obtain mixed powder;
pre-burning the obtained mixed powder at 800-1200 ℃ to obtain pre-burned powder;
pressing and molding the obtained pre-sintered powder and a binder to obtain a blank;
and (3) removing the glue from the obtained blank, and sintering at 1250-1350 ℃ for 2-6 hours to obtain the high-temperature stable medium ceramic material.
8. The method according to claim 7, wherein the Ca source is CaCO3The Si source is SiO2The Ti source is TiO2The M1 source is an oxide of M1 and the M2 source is an oxide of M2.
9. The production method according to claim 7 or 8, wherein the pre-firing system includes: the temperature is preserved for 2-5 hours at 800-1000 ℃, and then preserved for 4-8 hours at 1050-1200 ℃.
10. The method of claim 9, wherein the pre-firing schedule comprises: the temperature is firstly preserved for 2 hours at 900 ℃, and then the temperature is raised to 1150 ℃ and preserved for 6 hours.
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CN101172849A (en) * 2007-10-26 2008-05-07 华南理工大学 Low-temperature sintering high dielectric constant dielectric ceramic and method for producing the same
CN101928138A (en) * 2010-09-01 2010-12-29 郑州大学 Laser synthesis method of CaTiO3-CaTiSiO5
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