CN114242454A - Sodium bismuth titanate-based quaternary high-temperature stable high-dielectric lead-free ceramic capacitor dielectric material and preparation - Google Patents
Sodium bismuth titanate-based quaternary high-temperature stable high-dielectric lead-free ceramic capacitor dielectric material and preparation Download PDFInfo
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 32
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 26
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 4
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 26
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 14
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 13
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 13
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 11
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 239000007858 starting material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 239000003990 capacitor Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 6
- 239000006104 solid solution Substances 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 229910002059 quaternary alloy Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000003292 glue Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012071 phase Substances 0.000 description 6
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910010252 TiO3 Inorganic materials 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910003237 Na0.5Bi0.5TiO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1254—Ceramic dielectrics characterised by the ceramic dielectric material based on niobium or tungsteen, tantalum oxides or niobates, tantalates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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Abstract
A sodium bismuth titanate-based quaternary high-temperature stable high-dielectric lead-free ceramic capacitor dielectric material and a preparation method thereof are mainly applied to the field of electronic passive devices such as multilayer ceramic capacitors and the like. According to the expression (1-x) (0.64 Na)0.5Bi0.5TiO3‑0.16K0.5Bi0.5TiO3‑0.2SrTiO3)‑xBi(Mg2/3Nb1/3)O3X is 0.10, and Bi is weighed according to the stoichiometric ratio2O3，K2CO3，Na2CO3，TiO2，SrCO3，Nb2O5，Mg(OH)2As a starting material. Ball-milling and mixing the raw materials, drying, calcining the powder at high temperature, ball-milling for the second time, grinding into powder after drying, granulating by taking polyvinyl butyral alcohol solution as a binder, then sieving with a 120-mesh sieve, press-forming, removing glue, and then emptying in a high-temperature furnaceSintering in gas atmosphere, and naturally cooling to room temperature along with the furnace.
Description
Technical Field
The invention relates to a bismuth sodium titanate based quaternary system high-temperature stable high-dielectric lead-free ceramic capacitor material obtained by compounding a high-dielectric paraelectric body and a metastable ferroelectric body with a relaxation type ferroelectric body with a morphotropic phase boundary and a preparation method thereof. The method is mainly applied to the field of electronic passive devices such as multilayer ceramic capacitors and the like.
Background
The multilayer ceramic capacitor has the characteristics of small volume and large capacity, and is an indispensable basic element in various electronic devices. With the rapid development of 5G, electric vehicles, and smart manufacturing technologies, the demand for high-quality capacitors is rapidly increasing year by year. The existing large-capacity multilayer ceramic capacitor is mainly made of BaTiO3Is a matrix, and is difficult to stably operate in a high-temperature environment of 250 ℃ or higher even by doping modification because of its low intrinsic curie temperature (120 ℃). For space shuttles, hybrid vehicles and oil exploration equipment which operate under severe conditions, the development of high-temperature ceramic capacitors is of great importance, which is helpful for reducing the use of secondary cooling systems, thereby achieving the light weight and miniaturization of the whole machine.
Compared with BaTiO with low Curie temperature3，Na0.5Bi0.5TiO3Has high characteristic temperature (320 ℃) and the characteristic of dispersion phase transition, and is an important lead-free relaxation type ferroelectric. In recent years, some studies have found that Na can be adjusted by introducing metastable ferroelectric elements0.5Bi0.5TiO3Composition content of different types of Polar Nanodomains (PNR) in the base system. Thus, the thermal stability of high temperature ceramic dielectrics can be enhanced by weakening the ferroelectric coupling behavior. Recently, researchers have proposed the addition of metastable ferroelectric elements Bi (Mg)2/3Nb1/3)O3Modified Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3The composite system (NBT-KBT-BMN) realizes the capacitance temperature change rate delta C/C within the range of 112-410 DEG C150℃Less than or equal to +/-15 percent and THE dielectric loss is less than 2.5 percent (Xu Yuru et al, JOURNAL OF THE E EUROPEAN CERAMIC SOCIETY volume: 40 th phase: 13 page: 4487. year 4494 publication: 2020). However, it should be noted that the material has a standard dielectric constant of only 1860 at 150 ℃ while having excellent temperature stability. The low dielectric constant results in low volumetric efficiency of the capacitor, which is not conducive to the development of high-capacity high-temperature multilayer ceramic capacitors. Furthermore, this is achievedThe bismuth (Bi) content of the ceramic material is high (the mass percent of bismuth is 62.8%), the element has strong volatility at high temperature, the mismatch of the stoichiometric ratio of the ceramic and the non-uniform components are easily caused, and the process stability and the application in the aspect of multilayer ceramic capacitors are limited.
Disclosure of Invention
The technical problem to be solved by the invention is to simultaneously meet the capacitance temperature stability (Delta C/C) within the working temperature range for the existing high-temperature ceramic capacitor material150℃Not more than +/-15 percent) and low dielectric loss (tan delta is not more than 2.5 percent), and is difficult to keep higher dielectric constant and lower Bi element content, so as to provide a bismuth sodium titanate-based quaternary high-temperature stable high-dielectric lead-free ceramic capacitor material obtained by compounding a high-dielectric cis-conductor and a metastable ferroelectric with a morphotropic phase boundary and a preparation method thereof. The ceramic dielectric material can simultaneously ensure excellent capacitance temperature stability (delta C/C) in a high and wide temperature range (80-330℃)150℃+/-15%) and low dielectric loss (tan delta is less than or equal to 2.5%), and has a relative dielectric constant of about 3050 at a standard temperature of 150 ℃ and a bismuth mass percent as low as 51.9% at a test frequency of 1 kHz.
The invention is realized by the following technical scheme.
A high-temp, wide-temp and high-dielectric lead-free ceramic dielectric material for capacitor is prepared from (1-x) (0.64 Na)0.5Bi0.5TiO3-0.16K0.5Bi0.5TiO3-0.2SrTiO3)-xBi(Mg2/3Nb1/3)O3Wherein x is 0.10.
The working temperature range of the high-wide-temperature high-dielectric lead-free capacitor ceramic dielectric material is as follows: 80-330 ℃.
A preparation method of a novel dielectric material for a high-width-temperature high-dielectric lead-free multilayer ceramic capacitor comprises the following specific steps:
(1): preparing (1-x) (0.64 Na) by a conventional solid phase method0.5Bi0.5TiO3-0.16K0.5Bi0.5TiO3-0.2SrTiO3)-xBi(Mg2/3Nb1/3)O3A solid solution, wherein x is 0.10. Weighing proper amount of Bi2O3，K2CO3，Na2CO3，TiO2，SrCO3，Nb2O5，Mg(OH)2As a starting material, the material is dried for 8 hours at a temperature of 100 ℃;
(2): weighing Bi according to the stoichiometric ratio2O3，K2CO3，Na2CO3，SrCO3，Nb2O5，Mg(OH)2，TiO2And pouring the mixture into a ball milling tank in sequence, taking absolute ethyl alcohol as a ball milling medium, and carrying out ball milling on the mixture and zirconia balls for 12 hours in a planetary ball mill. After drying, the mixture was placed in an alumina crucible and calcined in air at 850 ℃ for 3 hours at a rate of 4 ℃/min.
(3): and (3) placing the powder calcined in the step (2) into a ball milling tank for ball milling for 12 hours again. Drying, grinding into powder, granulating with polyvinyl butyral (PVB) as binder, sieving with 120 mesh sieve, and pressing under 200MPa uniaxial pressure to obtain wafer. Keeping the temperature at 650 ℃ for 4 hours to discharge colloid, embedding the wafer into calcined powder with the same components, and then keeping the temperature at 1050 ℃ for 3 hours to obtain the novel high-width-temperature high-dielectric lead-free multilayer ceramic capacitor dielectric material.
The calcined powder of the same composition means the calcined powder obtained in step (2).
Compared with the prior art, the invention has the following advantages:
the method solves the problem that the temperature stability range (delta C/C) of the traditional dielectric material taking barium titanate as a matrix150℃Less than or equal to +/-15 percent, and tan delta less than or equal to 2.5 percent) is difficult to reach the temperature of more than 250 ℃. Simultaneously improves the low dielectric constant of the reported bismuth sodium titanate-based high-wide-temperature ceramic capacitor material<2000) The content of volatile Bi is high. The system successfully controls the content of Bi element to be lower, and the mass percent of bismuth is as low as 51.9%. The obtained ceramic material has excellent dielectric constant performance, the relative dielectric constant of the ceramic material is far higher than that of other high-temperature capacitor ceramic dielectric materials (reaching about 3050), and the temperature stability regionThe temperature can be kept between 80 ℃ and 330 ℃. The material does not contain substances harmful to the environment, has low cost of raw materials and simple preparation process, and has good application prospect.
Drawings
The phase structure of the sample is measured by an X-ray diffractometer model D8-Advance of Bruker company in Germany, and the microscopic morphology of the prepared material is measured by a Hitachi S-4800 scanning electron microscope. The precise digital bridge (Agilent E4980A) is adopted to connect an automatic temperature control device, and the dielectric constant and the dielectric loss of the dielectric material in the temperature range of 25-500 ℃ are tested at 1 kHz.
FIG. 1: XRD patterns of the ceramic dielectric materials prepared in example 1 and comparative examples 1, 2, and 3.
FIG. 2: scanning electron micrographs of sections of the ceramic dielectric materials prepared in example 1 and comparative examples 1, 2 and 3.
FIG. 3: the temperature change rate versus temperature curves for the ceramic dielectric materials prepared in example 1 and comparative examples 1, 2, and 3.
FIG. 4: the dielectric constant and dielectric loss versus temperature curves for the ceramic dielectric material prepared in example 1 were measured at a frequency of 1 kHz.
FIG. 5: the dielectric constant and dielectric loss versus temperature curve of the ceramic dielectric material prepared in comparative example 1 at a frequency of 1 kHz.
FIG. 6: the dielectric constant and dielectric loss versus temperature curve of the ceramic dielectric material prepared in comparative example 2 at a frequency of 1 kHz.
FIG. 7: the dielectric constant and dielectric loss versus temperature curve of the ceramic dielectric material prepared in comparative example 3 at a frequency of 1 kHz.
Wherein, a, b, c and d in the scanning electron microscope represent specific example 1, comparative example 2 and comparative example 3 respectively.
Detailed Description
The present invention will be further illustrated by the following examples in conjunction with comparative examples, but the present invention is not limited to the following examples.
Example 1
(1): preparing (1-x) (0.64 Na) by a conventional solid phase method0.5Bi0.5TiO3-0.16K0.5Bi0.5TiO3-0.2SrTiO3)-xBi(Mg2/3Nb1/3)O3A solid solution, wherein x is 0.10. Weighing proper amount of Bi2O3，K2CO3，Na2CO3，TiO2，SrCO3，Nb2O5，Mg(OH)2As a starting material, the material is dried for 8 hours at a temperature of 100 ℃;
(2): weighing Bi according to the stoichiometric ratio2O3，K2CO3，Na2CO3，SrCO3，Nb2O5，Mg(OH)2，TiO2And pouring the mixture into a ball milling tank in sequence, taking absolute ethyl alcohol as a ball milling medium, and carrying out ball milling on the mixture and zirconia balls for 12 hours in a planetary ball mill. After drying, the mixture was placed in an alumina crucible and calcined in air at 850 ℃ for 3 hours at a rate of 4 ℃/min.
(3): and (3) placing the powder calcined in the step (2) into a ball milling tank for ball milling for 12 hours again. Drying, grinding into powder, granulating with polyvinyl butyral (PVB) as binder, sieving with 120 mesh sieve, and pressing under 200MPa uniaxial pressure to obtain wafer. Keeping the temperature at 650 ℃ for 4 hours to discharge colloid, embedding the wafer into calcined powder with the same components, and then keeping the temperature at 1050 ℃ for 3 hours to obtain the novel dielectric material a for the high-width-temperature high-dielectric lead-free multilayer ceramic capacitor.
Comparative example 1
(1): preparing (1-x) (0.64 Na) by a conventional solid phase method0.5Bi0.5TiO3-0.16K0.5Bi0.5TiO3-0.2SrTiO3)-xBi(Mg2/3Nb1/3)O3A solid solution, wherein x is 0. Weighing proper amount of Bi2O3，K2CO3，Na2CO3，TiO2，SrCO3As a starting material, the material is dried for 8 hours at a temperature of 100 ℃;
(2): weighing Bi according to the stoichiometric ratio2O3，K2CO3，Na2CO3，SrCO3，TiO2And pouring the mixture into a ball milling tank in sequence, taking absolute ethyl alcohol as a ball milling medium, and carrying out ball milling on the mixture and zirconia balls for 12 hours in a planetary ball mill. After drying, the mixture was placed in an alumina crucible and calcined in air at 850 ℃ for 3 hours at a rate of 4 ℃/min.
(3): and (3) placing the powder calcined in the step (2) into a ball milling tank for ball milling for 12 hours again. Drying, grinding into powder, granulating with polyvinyl butyral (PVB) as binder, sieving with 120 mesh sieve, and pressing under 200MPa uniaxial pressure to obtain wafer. Keeping the temperature at 650 ℃ for 4 hours to discharge colloid, embedding the wafer into calcined powder (the calcined powder obtained in the step (2)) with the same components, and then keeping the temperature at 1050 ℃ for 3 hours to obtain the novel dielectric material b for the high-width-temperature high-dielectric lead-free multilayer ceramic capacitor.
Comparative example 2
(1): preparing (1-x) (0.64 Na) by a conventional solid phase method0.5Bi0.5TiO3-0.16K0.5Bi0.5TiO3-0.2SrTiO3)-xBi(Mg2/3Nb1/3)O3A solid solution, wherein x is 0.05. Weighing proper amount of Bi2O3，K2CO3，Na2CO3，TiO2，SrCO3，Nb2O5，Mg(OH)2As a starting material, the material is dried for 8 hours at a temperature of 100 ℃;
(2): weighing Bi according to the stoichiometric ratio2O3，K2CO3，Na2CO3，SrCO3，Nb2O5，Mg(OH)2，TiO2And pouring the mixture into a ball milling tank in sequence, taking absolute ethyl alcohol as a ball milling medium, and carrying out ball milling on the mixture and zirconia balls for 12 hours in a planetary ball mill. After drying, the mixture was placed in an alumina crucible and calcined in air at 850 ℃ for 3 hours at a rate of 4 ℃/min.
(3): and (3) placing the powder calcined in the step (2) into a ball milling tank for ball milling for 12 hours again. Drying, grinding into powder, granulating with polyvinyl butyral (PVB) as binder, sieving with 120 mesh sieve, and pressing under 200MPa uniaxial pressure to obtain wafer. Keeping the temperature at 650 ℃ for 4 hours to discharge colloid, embedding the wafer into calcined powder (the calcined powder obtained in the step (2)) with the same components, and then keeping the temperature at 1050 ℃ for 3 hours to obtain the novel dielectric material c for the high-width-temperature high-dielectric lead-free multilayer ceramic capacitor.
Comparative example 3
(1): preparing (1-x) (0.64 Na) by a conventional solid phase method0.5Bi0.5TiO3-0.16K0.5Bi0.5TiO3-0.2SrTiO3)-xBi(Mg2/3Nb1/3)O3A solid solution, wherein x is 0.15. Weighing proper amount of Bi2O3，K2CO3，Na2CO3，TiO2，SrCO3，Nb2O5，Mg(OH)2As a starting material, the material is dried for 8 hours at a temperature of 100 ℃;
(2): weighing Bi according to the stoichiometric ratio2O3，K2CO3，Na2CO3，SrCO3，Nb2O5，Mg(OH)2，TiO2And pouring the mixture into a ball milling tank in sequence, taking absolute ethyl alcohol as a ball milling medium, and carrying out ball milling on the mixture and zirconia balls for 12 hours in a planetary ball mill. After drying, the mixture was placed in an alumina crucible and calcined in air at 850 ℃ for 3 hours at a rate of 4 ℃/min.
(3): and (3) placing the powder calcined in the step (2) into a ball milling tank for ball milling for 12 hours again. Drying, grinding into powder, granulating with polyvinyl butyral (PVB) as binder, sieving with 120 mesh sieve, and pressing under 200MPa uniaxial pressure to obtain wafer. Keeping the temperature at 650 ℃ for 4 hours to discharge colloid, embedding the wafer into calcined powder (the calcined powder obtained in the step (2)) with the same components, and then keeping the temperature at 1050 ℃ for 3 hours to obtain the novel dielectric material d for the high-width-temperature high-dielectric lead-free multilayer ceramic capacitor.
As can be seen from fig. 1, the prepared ceramic samples all exhibited a perovskite structure, and no second phase was generated.
As can be seen from fig. 2, the prepared ceramic samples all exhibited a dense microstructure with fewer defects.
As can be seen from FIG. 3, along with Bi (Mg)2/3Nb1/3)O3The content is increased, and the capacitance change rate satisfies the delta C/C150℃The temperature stability interval less than or equal to +/-15 percent is widened. When x is 0.10, the dielectric material has good capacitance temperature stability in the temperature range from 75 ℃ to 330 ℃.
As can be seen from fig. 4, when x is 0.10, the dielectric constant of the dielectric material has good temperature stability in the temperature range of 75 ℃ to 330 ℃, and the dielectric loss of the material is less than 2.5% in the temperature range of 80 ℃ to 340 ℃.
As can be seen from fig. 5 and 6, when x is 0 and x is 0.05, the dielectric material has a higher relative dielectric constant (>4000) at 150 ℃, but the temperature overlap interval between the temperature stability of the relative dielectric constant and the low dielectric loss is narrow, which is not suitable for the preparation of high-temperature and wide-temperature multilayer ceramic capacitors, compared to the sample where x is 0.10.
As can be seen from fig. 7, when x is 0.15, the dielectric constant of the dielectric material has good temperature stability in the temperature range of 85 ℃ to 365 ℃, and the dielectric loss of the material is less than 2.5% in the temperature range of 80 ℃ to 445 ℃. However, this material has a low dielectric constant (<2400), which is not favorable for increasing the capacitance of the capacitor.
Claims (5)
1. The high-dielectric lead-free ceramic capacitor dielectric material with the high-temperature stability of the sodium bismuth titanate-based quaternary system is characterized by comprising the chemical composition of (1-x) (0.64 Na)0.5Bi0.5TiO3-0.16K0.5Bi0.5TiO3-0.2SrTiO3)-xBi(Mg2/3Nb1/3)O3Wherein x is 0.10.
2. The preparation method of the bismuth sodium titanate-based quaternary high-temperature stable high-dielectric lead-free ceramic capacitor dielectric material as claimed in claim 1, is characterized by comprising the following steps:
(1): by using conventional techniquesPreparing (1-x) (0.64 Na) by solid phase method0.5Bi0.5TiO3-0.16K0.5Bi0.5TiO3-0.2SrTiO3)-xBi(Mg2/3Nb1/3)O3A solid solution, wherein x is 0.10. Weighing proper amount of Bi2O3，K2CO3，Na2CO3，TiO2，SrCO3，Nb2O5，Mg(OH)2As a starting material, the material is dried for 8 hours at a temperature of 100 ℃;
(2): weighing Bi according to the stoichiometric ratio2O3，K2CO3，Na2CO3，SrCO3，Nb2O5，Mg(OH)2，TiO2And pouring the mixture into a ball milling tank in sequence, taking absolute ethyl alcohol as a ball milling medium, and carrying out ball milling on the mixture and zirconia balls for 12 hours in a planetary ball mill. After drying, the mixture is put into an alumina crucible and calcined in the air for 3 hours at 850 ℃, and the heating rate is 4 ℃/min;
(3): and (3) placing the powder calcined in the step (2) into a ball milling tank for ball milling for 12 hours again. Drying, grinding into powder, granulating with polyvinyl butyral (PVB) as binder, sieving with 120 mesh sieve, and pressing under 200MPa uniaxial pressure to obtain wafer; keeping the temperature at 650 ℃ for 4 hours to discharge colloid, embedding the wafer into calcined powder with the same components, and then keeping the temperature at 1050 ℃ for 3 hours to obtain the dielectric material for the high-width-temperature high-dielectric lead-free multilayer ceramic capacitor.
3. The method for preparing the bismuth sodium titanate-based quaternary high-temperature stable high-dielectric lead-free ceramic capacitor dielectric material as claimed in claim 2, wherein the calcined powder with the same components refers to the calcined powder obtained in the step (2).
4. The application of the bismuth sodium titanate-based quaternary high-temperature stable high-dielectric lead-free ceramic capacitor dielectric material as claimed in claim 1, wherein the working temperature range is as follows: 80-330 ℃.
5. Use according to claim 4, for ensuring at the same time an excellent temperature stability Δ C/C of the capacitor in the operating temperature range150℃Less than or equal to 15 percent and low dielectric loss tan delta less than or equal to 2.5 percent, under the test frequency of 1kHz, the relative dielectric constant of 150 ℃ at the standard temperature is about 3050, and the mass percent of bismuth is as low as 51.9 percent.
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