CN106938928A - A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material - Google Patents

A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material Download PDF

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CN106938928A
CN106938928A CN201710206586.0A CN201710206586A CN106938928A CN 106938928 A CN106938928 A CN 106938928A CN 201710206586 A CN201710206586 A CN 201710206586A CN 106938928 A CN106938928 A CN 106938928A
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李玲霞
蔡朝阳
李江腾
张宁
王瑞杰
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Tianjin University
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Abstract

The invention discloses the anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material of one kind, with BaTiO3Powder is base-material, on this basis, and additional mass percent is 0.3~0.8% Na0.5Bi0.5TiO3；0.6~1.5% (NiO)1‑x(NbO2.5)x, wherein x=0.6~0.8；0.1~0.5% (MnO)1‑y(NbO2.5)y, wherein y=0.4~0.6；1.0~3.0% CaZrO3.First with BaTiO3As base-material, adulterate Na0.5Bi0.5TiO3, BT NBT mixtures are made；Again (NiO) is added in BT NBT1‑x(NbO2.5)x、(MnO)1‑y(NbO2.5)yAnd CaZrO3, compressing is green compact.1290~1315 DEG C of sintering in reducing atmosphere, ceramic capacitor dielectric material needed for being made.The present invention can prevent barium titanate semiconducting process, while lifting dielectric constant, ensureing that operation temperature area is wider, with relatively low dielectric loss and high insulation resistivity.In 55 DEG C~150 DEG C warm areas, rate of change of capacitance is within ± 10%, and with high room temperature dielectric constant (15000@1kHz) and low room temperature dielectric constant dielectric loss (tan=2.2%), the insulation resistivity of material is more than 2.0 × 1011Ω·cm。

Description

A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material
Technical field
The invention belongs to a kind of ceramic composition being characterized with composition, and in particular to one kind meets reducing atmosphere sintering will Ask and with huge dielectric constant, higher insulation resistivity, more low-loss temperature-stable X8R type ceramic capacitor dielectric materials And preparation method thereof.
Background technology
Electronics based on chip multilayer ceramic capacitor (Multilayer Ceramic Capacitor, abbreviation MLCC) Component, application field is extensive.Barium titanate (BaTiO3) base temperature-stable MLCC dielectric materials are because of its environmental sound, one It is directly the focus of research,
Traditional MLCC uses intermediate sintering temperature technique, and matching interior electrode is used is used as interior electricity with noble metals such as Pt, Pd Pole material, this occupies MLCC manufacturing costs 60%~70%.Develop with MLCC towards high capacity, its interior media number of plies increases Plus, inner electrode layer number is consequently increased, and MLCC manufacturing costs are improved constantly.Use nickel metal as interior electrode cost for silver-colored palladium electricity / 20th of pole, considerably reduces cost.Nickel metal inner electrode multilayer ceramic capacitor (Ni-MLCC) has resistivity It is low, reduce internal and external electrode equivalent resistance the advantages of, but need to sinter under reducing atmosphere with prevent nickel electrode be oxidized, BaTiO3 Semiconductor transformation occurs in sintering under reducing atmosphere, and insulation resistivity declines, and as semiconductor, loses dielectric behavior.Therefore make Ni-MLCC keys are to develop nickel electrode co-fire match anti-reduction material.
Huge dielectric constant (ε>103) dielectric material be make high-performance energy storage device ideal material, can be applicable to Gao Jie MLCC, the field such as solid-state super capacitor.Nowadays, the loss of most huge dielectric constant dielectric materials it is universal it is higher (> 0.1), insulation resistivity is not high, and regulation dielectric loss often brings the deterioration of temperature stability, it is difficult to apply.Therefore, prepare A kind of huge dielectric material of the high insulation resistivity of low-loss seems particularly significant.
The content of the invention
The purpose of the present invention, is to overcome existing barium phthalate base ceramic capacity to use nickel metal inner electrode and reducing atmosphere The semiconducting problem that lower sintering barium titanate occurs, and solve dielectric loss present in huge dielectric constant dielectric material and stability Between mismatch problem；Simultaneously, it is to avoid leaded, environmentally hazardous problem in production or synthesis component.There is provided one kind has Excellent dielectric properties and the huge dielectric constant X8R types medium material for multilayer ceramic capacitors of higher insulaion resistance and its preparation side Method.
The present invention is achieved by following technical solution.
A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material, with BaTiO3Powder is base Material, on this basis, additional mass percent are 0.3~0.8% Na0.5Bi0.5TiO3；0.6~1.5% (NiO)1-x (NbO2.5)x, wherein x=0.6~0.8；0.1~0.5% (MnO)1-y(NbO2.5)y, wherein y=0.4~0.6；1.0~ 3.0% CaZrO3；
Described Na0.5Bi0.5TiO3, it is by Na2CO3、Bi2O3And TiO2It is 1 by mole ratio:1:4 synthesis；
(NiO)1-x(NbO2.5)xCompound, is by NiO and Nb2O51-x in molar ratio：X/2, wherein x=0.6~ 0.8 synthesis；
(MnO)1-y(NbO2.5)yCompound, is by MnCO3、Nb2O51-y in molar ratio：Y/2, wherein y=0.4~ 0.6 synthesis
The CaZrO3By CaCO3And ZrO21: 1 synthesis in molar ratio；
The preparation method of the ceramic capacitor dielectric material, with following steps：
(1) Na is synthesized0.5Bi0.5TiO3
By Na2CO3、Bi2O3And TiO2It is 1 by mole ratio:1:4 carry out dispensing, and mixing and ball milling dries after 4 hours, crosses 40 Mesh sub-sieve, is calcined 4 hours in 950 DEG C, and Na is made0.5Bi0.5TiO3；
(2) (NiO) is synthesized1-x(NbO2.5)xCompound, wherein x=0.6~0.8
By NiO, Nb2O51-x in molar ratio：The dispensing of x/2, wherein x=0.6~0.8, raw material mixed with deionized water after ball Mill 4 hours, in 120 DEG C of drying, crosses 40 mesh sub-sieves, is calcined 2 hours in 1000 DEG C, then secondary ball milling 6 hours, drying, crosses 80 Mesh sub-sieve, is made (NiO)1-x(NbO2.5)x, wherein x=0.6~0.8；
(3) (MnO) is synthesized1-y(NbO2.5)yCompound, wherein y=0.4~0.6
By MnCO3、Nb2O51-y in molar ratio：The dispensing of y/2, wherein y=0.4~0.6, after raw material is mixed with deionized water Ball milling 4 hours, in 120 DEG C of drying, crosses 40 mesh sub-sieves, in 800~1000 DEG C of calcinings, then secondary ball milling 6 hours, drying, mistake 80 mesh sub-sieves, are made (MnO)1-y(NbO2.5)y, wherein y=0.4~0.6；
(4) CaZrO is synthesized3
By CaCO3、ZrO2In molar ratio 1:1 dispensing, raw material mixed with deionized water after ball milling 4 hours, dried in 120 DEG C, 40 mesh sub-sieves are crossed, are calcined 2 hours in 1000 DEG C, CaZrO is made3；
(5) with BaTiO3It is used as base-material, the Na for mass percent 0.3~0.6% of adulterating0.5Bi0.5TiO3, mixing and ball milling 4 is small When, drying is calcined 8 hours after 1050 DEG C, and BT-NBT mixtures are made；
(6) composition of following mass percents is added in BT-NBT：0.6~1.5% (NiO)1-x(NbO2.5)x, its Middle x=0.6~0.8；0.1~0.5% (MnO)1-y(NbO2.5)y, wherein y=0.4~0.6；1.0~3.0% CaZrO3, Matched somebody with somebody raw material mixed with deionized water after ball milling 4~8 hours, additional mass percent is 7% binding agent after drying, crosses 80 mesh Sub-sieve is granulated；
(7) the granulation powder of step (6) is pressed into green compact, after dumping, in the nitrogen that hydrogen percentages are 0%~5% 1290~1315 DEG C of sintering in hydrogen mixing reducing atmosphere, 40~120mL/min of gas flow rate is incubated 3 hours, anti-reduction is made huge Dielectric constant and low loss high value ceramic capacitor dielectric material.
The Na0.5Bi0.5TiO3Addition be 0.5wt%.
The green compact of the step (6) are 15 × 1~1.3mm of Ф disk green compact.
The green compact of the step (6) were warming up to 550 DEG C of dumpings through 3.5 hours, then rose to 1150 DEG C of sintering through 1 hour, protected Temperature 3 hours.
Beneficial effects of the present invention are as follows：
(1) ceramic capacitor dielectric material disclosed by the invention can be prevented in reduction by the doping vario-property to barium titanate The barium titanate semiconducting process sintered under atmosphere, is obviously improved the dielectric constant of dielectric material, it is ensured that dielectric material operation temperature area While wider, with relatively low dielectric loss and and high insulation resistivity.
(2) ceramic capacitor dielectric material disclosed by the invention has excellent dielectric properties：In -55 DEG C~150 DEG C temperature In area, rate of change of capacitance has high room temperature dielectric constant (~15000@1kHz) and low room temperature within ± 10% (tan=2.2%) is lost in K dielectric, and the insulation resistivity of material is more than 2.0 × 1011Ω·cm。
Embodiment
Below with reference to specific embodiment, the present invention is described in further detail：
Embodiment 1
First, the 2.6497g Na of pure level (>=99%) are analyzed with electronic balance weighing2CO3、11.6490g Bi2O3With 7.9898gTiO2Mixing, using deionized water as ball-milling medium, ball milling is dried after 4 hours, sieved, and is made in 950 DEG C of calcinings Na0.5Bi0.5TiO3；
By 2.2410g NiO and 9.3033g Nb2O5, mixing, using deionized water as ball-milling medium, ball milling dries after 4 hours Dry, sieving, is obtained (NiO) in 1000 DEG C of calcinings0.3(NbO2.5)0.7Compound, then secondary ball milling 6 hours, cross 80 mesh sub-sieves standby With；
The 5.7474g MnCO of pure level (>=99%) are analyzed with electronic balance weighing again3With 6.6452g Nb2O5, mixing, with Deionized water is as ball-milling medium, and ball milling is dried after 4 hours, sieved, and is obtained (MnO) in 900 DEG C of calcinings0.5(NbO2.5)0.5Chemical combination Thing, then secondary ball milling 6 hours, cross 80 mesh sub-sieves standby；
Again by 22.3291g CaCO3With 27.5114g ZrO2Mixing, using deionized water as ball-milling medium, ball milling 4 hours Dry, sieve afterwards, CaZrO is obtained in 1000 DEG C of calcinings3；
By 20g BaTiO3、0.18g(NiO)0.3(NbO2.5)0.7、0.04g(MnO)0.5(NbO2.5)0.5With 0.2g CaZrO3 Ball milling 4 hours after being mixed with deionized water, additional mass percent is 7% paraffin after drying, crosses the granulation of 80 mesh sub-sieves.
Shaping and sintering：
(1) powder after granulation is pressed into 15 × 1.2mm of Ф disk green compact under 3MPa, stream of nitrogen gas flow velocity is kept For 40ml/min, 1290 DEG C were warming up to through 6 hours, 3 hours are incubated, huge Jie's low-loss multilayer ceramic capacitor medium material is made Material.
Silver paste is uniformly coated in resulting product upper and lower surface, electrode is prepared through 850 DEG C of burning infiltrations, testing sample, test is made Dielectric properties and TC characteristics.
The raw material of specific embodiment is matched somebody with somebody and sintering condition refers to table 1.
Embodiment 2-6
Embodiment 2-6 and the preparation process condition of embodiment 1 be substantially the same manner as Example 1, and difference is in body in table 1 It is existing.
Table 1
The method of testing and detection device of the present invention is as follows：
(1) dielectric properties test (AC test signals：Frequency is 1kHz, and voltage is 1V)
Using the capacitance C and loss tan δ of HEWLETT PACKARD 4278A type capacitance tester test samples, and The dielectric constant of sample is calculated, computing formula is：
(2) TC characteristic tests
Utilize GZ-ESPEC MPC-710P types high/low temperature circulation incubator, the special survey of HM27002 type capacitor C-T/V characteristics Examination instrument and HEWLETT PACKARD 4278A are tested.Capacitance of the sample in -55 DEG C~150 DEG C of warm area is measured, is used Following formula calculate rate of change of capacitance：
The test result of the specific embodiment of the invention refers to table 2.
Table 2
The invention is not limited in above-described embodiment, the change of many details is possible, but therefore this do not run counter to this The scope and spirit of invention.

Claims (4)

1. a kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material, with BaTiO3Powder is base-material, On the basis of this, additional mass percent is 0.3~0.8% Na0.5Bi0.5TiO3；0.6~1.5% (NiO)1-x(NbO2.5)x, Wherein x=0.6~0.8；0.1~0.5% (MnO)1-y(NbO2.5)y, wherein y=0.4~0.6；1.0~3.0% CaZrO3；
Described Na0.5Bi0.5TiO3, it is by Na2CO3、Bi2O3And TiO2It is 1 by mole ratio:1:4 synthesis；
(NiO)1-x(NbO2.5)xCompound, is by NiO and Nb2O51-x in molar ratio：X/2, wherein x=0.6~0.8 are closed Into；
(MnO)1-y(NbO2.5)yCompound, is by MnCO3、Nb2O51-y in molar ratio：Y/2, wherein y=0.4~0.6 are closed Into
The CaZrO3By CaCO3And ZrO21: 1 synthesis in molar ratio.
The preparation method of the ceramic capacitor dielectric material, with following steps：
(1) Na is synthesized0.5Bi0.5TiO3
By Na2CO3、Bi2O3And TiO2It is 1 by mole ratio:1:4 carry out dispensing, and mixing and ball milling dries after 4 hours, crosses 40 mesh point Sample is sieved, and is calcined 4 hours in 950 DEG C, and Na is made0.5Bi0.5TiO3；
(2) (NiO) is synthesized1-x(NbO2.5)xCompound, wherein x=0.6~0.8
By NiO, Nb2O51-x in molar ratio：The dispensing of x/2, wherein x=0.6~0.8, ball milling 4 is small after raw material is mixed with deionized water When, in 120 DEG C of drying, 40 mesh sub-sieves are crossed, are calcined 2 hours in 1000 DEG C, then secondary ball milling 6 hours, drying, cross 80 mesh point sample Sieve, is made (NiO)1-x(NbO2.5)x, wherein x=0.6~0.8；
(3) (MnO) is synthesized1-y(NbO2.5)yCompound, wherein y=0.4~0.6
By MnCO3、Nb2O51-y in molar ratio：The dispensing of y/2, wherein y=0.4~0.6, raw material mixed with deionized water after ball milling 4 Hour, in 120 DEG C of drying, 40 mesh sub-sieves are crossed, in 800~1000 DEG C of calcinings, then secondary ball milling 6 hours, drying, 80 mesh point are crossed Sample is sieved, and is made (MnO)1-y(NbO2.5)y, wherein y=0.4~0.6；
(4) CaZrO is synthesized3
By CaCO3、ZrO2In molar ratio 1:1 dispensing, raw material mixed with deionized water after ball milling 4 hours, in 120 DEG C of drying, cross 40 Mesh sub-sieve, is calcined 2 hours in 1000 DEG C, and CaZrO is made3；
(5) with BaTiO3It is used as base-material, the Na for mass percent 0.3~0.6% of adulterating0.5Bi0.5TiO3, mixing and ball milling 4 hours, Drying is calcined 8 hours after 1050 DEG C, and BT-NBT mixtures are made；
(6) composition of following mass percents is added in BT-NBT：0.6~1.5% (NiO)1-x(NbO2.5)x, wherein x= 0.6~0.8；0.1~0.5% (MnO)1-y(NbO2.5)y, wherein y=0.4~0.6；1.0~3.0% CaZrO3, match somebody with somebody original Expect ball milling 4~8 hours after being mixed with deionized water, additional mass percent is 7% binding agent after drying, crosses 80 mesh sub-sieves Granulation；
(7) the granulation powder of step (6) is pressed into green compact, after dumping, mixed in hydrogen percentages for 0%~5% nitrogen hydrogen 1290~1315 DEG C of sintering in reducing atmosphere are closed, 40~120mL/min of gas flow rate is incubated 3 hours, anti-reduction giant dielectric is made Constant low loss, high value ceramic capacitor dielectric material.
2. the anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material of one kind according to claim 1, Characterized in that, the Na0.5Bi0.5TiO3Addition be 0.5wt%.
3. the anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material of one kind according to claim 1, Characterized in that, the green compact of the step (6) are 15 × 1~1.3mm of Ф disk green compact.
4. the anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material of one kind according to claim 1, Characterized in that, the green compact of the step (6) were warming up to 550 DEG C of dumpings through 3.5 hours, then rose to 1150 DEG C of sintering through 1 hour, Insulation 3 hours.
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