CN106673644A - SrTiO3 based energy storage medium material for medium temperature sintering - Google Patents

SrTiO3 based energy storage medium material for medium temperature sintering Download PDF

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CN106673644A
CN106673644A CN201710018433.3A CN201710018433A CN106673644A CN 106673644 A CN106673644 A CN 106673644A CN 201710018433 A CN201710018433 A CN 201710018433A CN 106673644 A CN106673644 A CN 106673644A
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parts
energy storage
modifying agent
storage medium
sintering
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CN106673644B (en
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杨魁勇
程华容
宋蓓蓓
齐世顺
吴爱忠
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Beijing Yuan Six Hongyuan Electronic Polytron Technologies Inc
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Beijing Yuan Six Hongyuan Electronic Polytron Technologies Inc
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Abstract

The invention discloses a SrTiO3 based energy storage medium material for medium temperature sintering. The material is prepared from the following components in parts by weight as follows: 100 parts of SrTiO3, 17.80-29.60 parts of CaTiO3, 7.30-20.30 parts of Bi2O3.3TiO2, 0.18-0.26 parts of MnCO3, 0.06-0.17 parts of Co2O3, 0.60-3.06 parts of MgTiO3, 0-0.15 parts of Y2O3, 0-0.18 parts of CeO2, 3.50-4.00 parts of a sintering aid. The SrTiO3 based energy storage medium material for medium temperature sintering can realize medium temperature sintering (at the sintering temperature of 1140-1160 DEG C), and has the advantages of higher dielectric constant (epsilon: 300-360), low loss (tan delta: 3-10*10<4>), high insulation resistivity (rho: 3.4-12.2*10<13>omega.cm), high breakdown voltage (higher than 280 kv/cm) and stable temperature coefficient (with a fluctuation range of plus or minus 500 ppm/DEG C). An MLCC (multi-layer ceramic capacitor) made of the energy storage medium material can meet the MLCC production process, and the MLCC has excellent comprehensive performance, good practical value and broad market prospect.

Description

A kind of strontium titanate base energy storage medium material for intermediate sintering temperature
Technical field
The present invention relates to electronic information material and component technical field, more particularly to a kind of metatitanic acid for intermediate sintering temperature Strontium base energy storage medium material, the material can be used for the MLCC productions of silver-palladium inner electrode intermediate sintering temperature.
Background technology
High energy storage density, high withstand voltage MLCC are one of common electronic components in electronic equipment, and it has discharge and recharge speed The extreme environment steady performances such as degree is fast, the strong, high temperature and high pressure of the anti-aging ability of circulation, in hybrid vehicle, arteries and veins The fields such as power power-supply, radar and Aero-Space are rushed to have broad application prospects.
High energy storage density and miniaturization are the development trends of energy storage ceramic capacitor, are mainly taken to tackle its development trend Measure：(1) capacitor arrangement is optimized, using multilayer ceramic capacitor structure；(2) dielectric material performance is improved, is such as improved and is situated between Electric constant, raising breakdown strength and reduce loss.At present, due to the limitation of equipment and technological level, it is difficult to make multilayer porcelain dielectric Structure of container is further enhanced.And develop high-k, breakdown strength high and low-loss and disclosure satisfy that current MLCC The dielectric material of manufacturing technique requirent is to realize high energy storage density and the effective path of miniaturization.
At present, the dielectric material for being commonly used for high voltage ceramic capacitor has：Barium titanate series, antiferroelectric media ceramic, titanium dioxide Titanium system and strontium titanate.Wherein, barium titanate ceramics have the advantages that dielectric constant is high, but its dielectric loss it is bigger than normal (1%~ 2%), breakdown potential force down (<100kV/cm) and it has electrostriction phenomena and limits the system in high-voltage capacitor field Application；Antiferroelectric media ceramic is mainly lead zirconate titanate system, and with dielectric constant is high, after applied voltage, dielectric constant rises etc. Advantage, but it is lead-containing materials, environmental pollution can be caused during production and use, with limiting the use of or disabling to lead-containing materials The implementation of relevant laws and regulations, the system is difficult to be widely used；TiO 2 series have breakdown voltage (≈ 350kV/cm) high, The advantages of dielectric loss low (≈ 0.05%), but dielectric constant low (≈ 110) is difficult to produce the capacitor of high energy storage density；Metatitanic acid Strontium system has the advantages that of a relatively high dielectric constant (≈ 250), high-frequency loss be low, breakdown strength high, additionally, strontium titanates normal temperature It is down paraelectrics structure, applying certain external electric field will not cause electricdomain to rotate, so as to improve the reliability of capacitor and use Life-span.
The content of the invention
Weak point present in regarding to the issue above, the present invention provides a kind of strontium titanate base energy storage for intermediate sintering temperature Dielectric material, the dielectric material has dielectric constant higher, breakdown strength and insulation resistivity, relatively low loss and sintering temperature Degree, and temperature coefficient stabilization and it is adjustable the advantages of..
To achieve the above object, the present invention provides a kind of strontium titanate base energy storage medium material for intermediate sintering temperature, Jie Material is made up of major ingredient, secondary material, modifying agent and sintering aid, wherein：
The major ingredient is SrTiO3；
The secondary material is CaTiO3And Bi2O3·3TiO2；
The modifying agent is MnCO3、MgTiO3、Co2O3、CeO2And Y2O3In three kinds or more；
The sintering aid BZS is by H3BO3, ZnO and SiO2Composition.
As a further improvement on the present invention, the dielectric material is with the SrTiO of 100 weight portions3It is base material, each composition and phase It is as follows to content：
Major ingredient SrTiO3It is 100 parts；
Pair material CaTiO3It is 17.80~29.60 parts；
Pair material Bi2O3·3TiO2It is 7.30~20.30 parts；
Sintering aid BZS is 3.50~4.00 parts；
Modifying agent MnCO3It is 0.18~0.26 part；
Modifying agent MgTiO3It is 0.60~3.06 part；
Modifying agent Co2O3It is 0~0.18 part；
Modifying agent Y2O3It is 0~0.15 part；
Modifying agent CeO2It is 0~0.18 part；
Above-mentioned each composition is weighed according to weight, is put into the ball grinder equipped with zirconia ball, addition deionized water ball milling, Drying, grinding sieving, pack standby.
Compared with prior art, beneficial effects of the present invention are：
A kind of strontium titanate base energy storage medium material for intermediate sintering temperature disclosed by the invention, is prepared using conventional solid-state method Go out strontium titanate ceramic material, it has dielectric constant higher, breakdown strength and insulation resistivity, relatively low loss and sintering Temperature, and temperature coefficient is stable and adjustable；The dielectric material can be used for the MLCC productions of silver-palladium inner electrode, and the material is carried out The process certification (30 μm ± 0.3 μm of tape casting diaphragm thickness) of MLCC, the manufacturability such as curtain coating and sintering is good, the MLCC's for being produced Excellent combination property, the dielectric material has good practical value and market prospects.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in the embodiment of the present invention Technical scheme is clearly and completely described, it is clear that described embodiment is a part of embodiment of the invention, rather than Whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not before creative work is made The every other embodiment for being obtained is put, the scope of protection of the invention is belonged to.
Selected raw material of the invention unless otherwise specified, can be purchased by commercial channel.
For problems of the prior art, the present invention uses conventional solid-state method combination doping vario-property technology, prepares Strontium titanate ceramic material, it has dielectric constant higher, breakdown strength and insulation resistivity, relatively low loss and sintering temperature Degree, and temperature coefficient is stable and adjustable, is a kind of very promising energy-storing dielectric ceramic material.
The present invention provides a kind of strontium titanate base energy storage medium material for intermediate sintering temperature, and the dielectric material is by major ingredient SrTiO3, secondary material CaTiO3And Bi2O3·3TiO2, modifying agent MnCO3、MgTiO3、Co2O3、CeO2And Y2O3In three kinds or three kinds Constituted with sintering aid BZS above, sintering aid BZS is by H3BO3, ZnO and SiO2Composition.Wherein：Major ingredient SrTiO3Quality point Number is 64.55wt%-75.23wt%, and the dielectric material is with the SrTiO of 100 weight portions3It is base material, each composition and relative amount It is as follows：Major ingredient SrTiO3It is 100 parts, secondary material CaTiO3It is 17.80~29.60 parts, secondary material Bi2O3·3TiO2It is 7.30~20.30 Part, sintering aid BZS are 3.50~4.00 parts, modifying agent MnCO3It is 0.18~0.26 part, modifying agent MgTiO3For 0.60~ 3.06 parts, modifying agent Co2O3It is 0~0.18 part, modifying agent Y2O3It is 0~0.15 part and modifying agent CeO2It is 0~0.18 part.Its In, major ingredient, secondary material and sintering aid are prepared using analytically pure industrial chemicals.The major ingredient SrTiO3It is paraelectrics structure, Pair material CaTiO3And Bi2O3·3TiO2Temperature coefficient and dielectric constant for adjusting the dielectric material, modifying agent are used to optimize Comprehensive electrical performance, sintering aid is used to reduce sintering temperature, it is final obtain temperature coefficient seriation and stabilization for middle temperature Sinter the strontium titanate base energy storage medium material of excellent combination property.
A kind of preparation method of strontium titanate base energy storage medium material for intermediate sintering temperature of the invention is：
(1), with analytically pure SrCO3And TiO2It is raw material, in molar ratio 1:1 weighs SrCO3And TiO2Raw material, will weigh Raw material be put into the ball grinder equipped with zirconia ball, carry out mixing and ball milling, ball milling 7~9 hours by medium of deionized water；So Dry in an oven afterwards, drying temperature is 110~120 DEG C, drying time 6~8 hours；Again in Muffle furnace 1100 ± 20 DEG C forge Burning obtains major ingredient SrTiO in 2.5 hours3Powder.
(2), with analytically pure CaCO3And TiO2It is raw material, in molar ratio 1:1 weighs CaCO3And TiO2Raw material, will weigh Raw material be put into the ball grinder equipped with zirconia ball, mixing and ball milling is carried out by medium of deionized water, 5~6 hours when being；So Dry in an oven afterwards, drying temperature is 110~120 DEG C, drying time 6~8 hours；Again in Muffle furnace 1050 ± 20 DEG C forge Burning obtains secondary material CaTiO for 2.5 hours3Powder.
(3), with analytically pure Bi2O3And TiO2It is raw material, in molar ratio 1:3 weigh Bi2O3And TiO2Raw material, by what is weighed Raw material is put into the ball grinder equipped with zirconia ball, and mixing and ball milling is carried out by medium of deionized water, 5~6 hours when being；Then Dry in an oven, drying temperature is 110~120 DEG C, drying time 6~8 hours；880 DEG C ± 30 calcinings 2 in Muffle furnace again Hour obtains secondary material Bi2O3·3TiO2Powder.
(4) H in sintering aid BZS please, be supplement3BO3, ZnO and SiO2With when preparation method according to mass ratio 1:2.3: 0.7 ratio weighs H3BO3, ZnO and SiO2；From deionized water as ball-milling medium, Ball-milling Time is 5 hours；Drying temperature It it is 85 DEG C, the time is 10 hours, and 80 mesh sieves are crossed afterwards；Calcined temperature is 570 DEG C, and the time is 5 hours, afterwards furnace cooling；Through After crossing grinding, 100 mesh sieves are crossed, obtain the sintering aid BZS, and be packaged with valve bag and store for future use.
(5), according to the weight of table 1 than carrying out the weighing of major ingredient, secondary material, modifying agent and sintering aid (unit for gram), with Deionized water is medium, and ball milling mixing 5 hours is dried 6 hours at 120 DEG C, takes out ceramic powder, grinds and cross 40 mesh sieves Afterwards, encapsulated with valve bag and stored.
The dielectric material recipe list of table 1
Performance Assessment is carried out to prepared ceramic material：2g ceramic powders are weighed, adds the PVA aqueous solution of 6.5wt% to enter Row granulation, is pressed into the disk of Ф=10mm under 200MPa, is put into resistance furnace, is increased to by room temperature with 2~3 DEG C/min 500~600 DEG C, 2~3 hours dumpings of insulation, then be increased to 1150 DEG C ± 10 DEG C with 4~5 DEG C/min and sinter porcelain, furnace cooling into Afterwards, carry out sample surfaces treatment, and coat, sintered electrode.Be made after wafer capacitance device test capacitance, loss, insulaion resistance and Breakdown voltage, and calculate relative dielectric constant, insulation resistivity and disruptive field intensity；And test its temperature characterisitic, its electricity Performance parameter is shown in Table 2.
The dielectric material disk capabilities list of table 2
Using 7 corresponding ceramic materials of formula 1 and formula, through dispensing, curtain coating, printing, lamination, even pressure, dumping, sintering (1150 DEG C of sintering temperature), chamfering, Tu Duan, burning end, plating obtain MLCC chips (the average medium thickness degree that capacity is 220nF 20μm).MLCC electric properties are as shown in table 3.
The dielectric material chip performance of table 3
A kind of strontium titanate base energy storage medium material for intermediate sintering temperature of the invention, metatitanic acid is prepared using conventional solid-state method Strontium base ceramic material, it has dielectric constant higher, breakdown strength and insulation resistivity, relatively low loss and sintering temperature, And temperature coefficient is stable and adjustable.The dielectric material can be used for the MLCC productions of silver-palladium inner electrode, and the material has carried out MLCC's Process certification (30 μm ± 0.3 μm of tape casting diaphragm thickness), the manufacturability such as curtain coating and sintering is good, and the MLCC's for being produced is comprehensive Can be excellent, the dielectric material has good practical value and market prospects.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses the present invention. Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the present invention.Therefore, the present invention will not be by It is limited to the embodiments shown herein, and is to fit to consistent with principles disclosed herein and features of novelty most wide Scope.

Claims (2)

1. a kind of strontium titanate base energy storage medium material for intermediate sintering temperature, it is characterised in that the dielectric material is by major ingredient, pair Material, modifying agent and sintering aid composition, wherein：
The major ingredient is SrTiO3；
The secondary material is CaTiO3And Bi2O3·3TiO2；
The modifying agent is MnCO3、MgTiO3、Co2O3、CeO2And Y2O3In three kinds or more；
The sintering aid BZS is by H3BO3, ZnO and SiO2Composition.
2. the strontium titanate base energy storage medium material of intermediate sintering temperature is used for as claimed in claim 1, it is characterised in that the medium material Material is with the SrTiO of 100 weight portions3It is base material, each composition and relative amount are as follows：
Major ingredient SrTiO3It is 100 parts；
Pair material CaTiO3It is 17.80~29.60 parts；
Pair material Bi2O3·3TiO2It is 7.30~20.30 parts；
Sintering aid BZS is 3.50~4.00 parts；
Modifying agent MnCO3It is 0.18~0.26 part；
Modifying agent MgTiO3It is 0.60~3.06 part；
Modifying agent Co2O3It is 0~0.18 part；
Modifying agent Y2O3It is 0~0.15 part；
Modifying agent CeO2It is 0~0.18 part；
Above-mentioned each composition is weighed according to weight, is put into the ball grinder equipped with zirconia ball, added deionized water ball milling, dry Dry, grinding sieving, packs standby.
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