CN107344851A - A kind of wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free and preparation method thereof - Google Patents
A kind of wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free and preparation method thereof Download PDFInfo
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- CN107344851A CN107344851A CN201710496511.0A CN201710496511A CN107344851A CN 107344851 A CN107344851 A CN 107344851A CN 201710496511 A CN201710496511 A CN 201710496511A CN 107344851 A CN107344851 A CN 107344851A
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- 239000000463 material Substances 0.000 title claims abstract description 82
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 45
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000011734 sodium Substances 0.000 claims abstract description 50
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 28
- 229910003334 KNbO3 Inorganic materials 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 23
- 238000007873 sieving Methods 0.000 claims abstract description 21
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 239000004332 silver Substances 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 239000002003 electrode paste Substances 0.000 claims abstract description 8
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 33
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 24
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 17
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 7
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 6
- 229910002367 SrTiO Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 20
- 239000000919 ceramic Substances 0.000 description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 230000002159 abnormal effect Effects 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000005498 polishing Methods 0.000 description 10
- 238000002367 polarised neutron reflectometry Methods 0.000 description 6
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 229910003080 TiO4 Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/475—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on bismuth titanates
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- 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
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Abstract
The present invention relates to wide temperature area temperature stabilizing type ceramic capacitor material of a kind of bismuth-sodium titanate base lead-free and preparation method thereof, first according to stoichiometric equation (1 x) (Bi0.5Na0.5)0.5Sr0.5TiO35wt%MgO xKNbO3, x=0.03~0.09, take SrTiO3Powder, Bi0.5Na0.5TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing；Full dispensing is subjected to ball milling, drying, sieving, obtains sieving materials；Sieving materials are compressing, 3~4 hours then are incubated at 1240~1250 DEG C, sintering obtains sintered specimen；Silver electrode paste is uniformly coated in sintered specimen tow sides, then is sintered to obtain the wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free.Ceramic capacitor material produced by the present invention, there is good temperature stability, and be applied to wide warm area, be advantageous to the use of ceramic capacitor material in particular circumstances.
Description
Technical field
The present invention relates to ceramic capacitor material field, and in particular to a kind of wide temperature area temperature stabilizing of bismuth-sodium titanate base lead-free
Type ceramic capacitor material and preparation method thereof.
Background technology
Informational function ceramics are one, and to be related to microelectronics, material science, physics, chemistry, electronics and mechanics etc. more
The field of subject crossing, is current development a kind of novel inorganic nonmetallic materials the rapidest and active, and prospect is very wide.
A series of great discoveries and invention in 20 century Solid State Electronics field, flourishing for information electronic industries is promoted, so as to
Human society has been started the process of IT application, accelerate the development of informational function ceramics.Pass through information material science and modern times
The combination of information technology, the novel slice type component for making all kinds of miniaturizations, Composite, high performance is obtained into more quantum jump with entering
Exhibition.Ceramic capacitor then important a member as electronics and information industry.
With deepening continuously for Science Explorations, the requirement to the temperature in use of electronic product is also increasingly harsher, this
Under the conditions of, the performance of ceramic capacitor material is also required to reach higher stability.It is even more to require strict in particular circumstances,
Having specially required electronic equipment operation at a high temperature of normal temperature is substantially exceeded also has high stability.Therefore, gone in itself from material
The finding the temperature span for widening ceramic capacitor material energy normal work of the task has put on schedule by people.
For manufacturing the dielectric material system of ceramic capacitor, be broadly divided into perovskite system, lead-based perovskite system with
And tungsten bronze structure system.Wherein bismuth-sodium titanate (Bi0.5Na0.5TiO3, BNT) system be used as with high-k, cheap, ring
The system of the advantages that guarantor, produced applied to commercialized ceramic capacitor.But although the system dielectric constant is high, Curie's temperature
Spend higher (~320 DEG C), dielectric properties are excessive to the dependence of temperature, and especially across after Curie temperature, descending grade is more
It is precipitous, therefore, scientist has carried out numerous studies to itself and composite, it is desirable to obtains more stable temperature characterisitic.For
Further reduction Curie temperature, SrTiO3(ST) it is a kind of typical low Curie temperature (~250 DEG C) dielectric material, has low
Dielectric loss, and BNT and ST is all ABO3The perovskite structure of type, it is possible to achieve doping solid solution.Chenwei Cui([1]
Chenwei Cui,Yongping Pu,Ziyan Gao,Jing Wan,Yisong Guo,Chiyuan Hui,Yaru Wang,
Yongfei Cui,Structure,dielectric and relaxor properties in lead-free ST-NBT
ceramics for high energy storage applications,Journal of Alloys and
Compounds.711 (2017) 319-326.) et al. have studied NBT-ST performance, find in Bi0.5Na0.5TiO3Middle addition ST
Really Curie temperature can be effectively reduced, but its dielectric properties is still larger to the dependence of temperature, and it is steady not meet temperature
Qualitatively require.Therefore, it is necessary to it is further composite modified to system ceramics progress, comply with X8R, or even X9R temperature
Stable type standard, and keep higher dielectric constant and relatively low dielectric loss.
The content of the invention
It is an object of the invention to take the defects of above-mentioned prior art is present, there is provided a kind of wide warm area of bismuth-sodium titanate base lead-free
Temperature-stable ceramic capacitor material and preparation method thereof, the ceramic capacitor material that profit is obtained by the present invention, no
But there is good temperature stability in wide warm area, and higher dielectric constant and relatively low dielectric loss, preparation technology
Simply, the cost of material is low, environment-friendly.
To reach above-mentioned purpose, the technical scheme of material of the present invention is：
The stoichiometric equation of the wide temperature area temperature stabilizing type ceramic capacitor material of described bismuth-sodium titanate base lead-free is (1-x)
(Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3, wherein x=0.03~0.09.
Preparation method of the present invention adopts the following technical scheme that：Comprise the following steps：
Step 1：According to stoichiometric equation (1-x) (Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3, x=0.03
~0.09, take SrTiO3Powder, Bi0.5Na0.5TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing；
Step 2：The full dispensing that step 1 is obtained carries out ball milling, drying, sieving, obtains sieving materials；
Step 3：The sieving materials that step 2 is obtained are compressing, are then incubated 3~4 hours at 1240~1250 DEG C, burn
Knot obtains sintered specimen；
Step 4：Silver electrode paste is uniformly coated in the sintered specimen tow sides that step 3 obtains, then is sintered
To the wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free.
Further, SrTiO in step 13The preparation process of powder includes：It is first according to mol ratio 1:1 weighs SrCO3With
TiO2It is mixed to form mixture A；Then mixture A, zirconium oxide ballstone and deionized water are taken, is 1 according to mass ratio:2:(0.7~
1) ball milling, drying and briquetting are carried out successively after mixing, and are most incubated 3~3.5 hours after 1130~1150 DEG C, are obtained pure phase
SrTiO3Powder.
Further, Bi in step 10.5Na0.5TiO3The preparation process of powder includes：It is first according to mol ratio 1:1:4 claim
Take Bi2O3、Na2CO3And TiO2It is mixed to form mixture B；Then mixture B, zirconium oxide ballstone and deionized water are taken, according to quality
Than for 1:2:(1.5~2) ball milling, drying and briquetting are carried out successively after mixing, it is most small after 845~855 DEG C of insulations 4.5~5.5
When, obtain the Bi of pure phase0.5Na0.5TiO3Powder.
Further, KNbO in step 13The preparation process of powder includes：It is first according to mol ratio 1:1 weighs Nb2O5With
K2CO3It is mixed to form mixture C；Then mixture C, zirconium oxide ballstone and deionized water are taken, is 1 according to mass ratio:2:(1~
1.2) ball milling, drying and briquetting are carried out successively after mixing, and are most incubated 2~2.5 hours after 800~810 DEG C, are obtained pure phase
KNbO3Powder.
Further, in step 2 by full dispensing and zirconium oxide ballstone, deionized water, according to mass ratio 1:(2~2.2):
(0.8~1) ball milling is carried out after mixing.
Further, the Ball-milling Time in step 2 is 18~24h.
Further, it is 120 mesh grit number to be crossed in step 2.
Further, sieving materials are compressing by isostatic cool pressing under 210~220MPa pressure in step 3, burn
Knot condition is：300 DEG C are warming up to 2 DEG C/min first, then 500~520 DEG C are warming up to 3 DEG C/min, then with 5 DEG C/min liters
Temperature is incubated 3~4 hours at 1240~1250 DEG C；Afterwards, 1000 DEG C are cooled to 3 DEG C/min, then are cooled to 5 DEG C/min
500~520 DEG C, finally cool to room temperature with the furnace.
Further, the sintering condition in step 4 is：15~30min is sintered at a temperature of 550~600 DEG C.
Compared with prior art, the present invention has technique effect beneficial below：
The present invention is by adding MgO, to increase the disruptive field intensity of material；Pass through KNbO3Doping concentration change, introduce ST this
The material of the low Curie temperature of class forms the wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free, not only with good
Good temperature stability, and it is applied to wide warm area, be advantageous to the use of ceramic capacitor material in particular circumstances, and
High dielectric constant and low dielectric loss are remain, for the present invention as x=0.03, dielectric constant is up to 1500.For ceramics
Capacitor material, relatively high dielectric constant and relatively low dielectric loss can keep good temperature stabilization in wider warm area
Property, it is that researchers pursue comparatively ideal result.The present invention is in KNbO3It is obtained when doping concentration is 0.03~0.05
Ceramic capacitor material meet X9R characteristics, i.e., when temperature range is -55~200 DEG C, temperature coefficient of capacitance is ± 15%；
KNbO3When doping concentration is more than 0.05, obtained ceramic capacitor material meets X8R characteristics, i.e., temperature range be -55~
At 150 DEG C, temperature coefficient of capacitance is ± 15%.
Preparation technology of the present invention is simple, and the cost of material is low, green, turns into replacement lead base ceramic material and is used as high-end work
Industry application material excellent important candidate material simultaneous technically and economically.
Brief description of the drawings
Fig. 1 is (1-x) (Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3The XRD of system ceramics；
Fig. 2 is 0.97 (Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-0.03KNbO3System ceramic dielectric constant (dielectric
Loss)-temperature curve；
Fig. 3 is 0.95 (Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-0.05KNbO3System ceramic dielectric constant (dielectric
Loss)-temperature curve；
Fig. 4 is 0.93 (Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-0.07KNbO3System ceramic dielectric constant (dielectric
Loss)-temperature curve；
Fig. 5 is 0.91 (Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-0.09KNbO3System ceramic dielectric constant (dielectric
Loss)-temperature curve；
Fig. 6 is (1-x) (Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3System ceramic dielectric constant-temperature is bent
Line；
Fig. 7 is (1-x) (Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3System ceramics temperature coefficient of capacitance-temperature
Curve.
Embodiment
Embodiments of the present invention are described in further detail below：
A kind of wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free, its stoichiometric equation are (1-x)
(Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3, wherein x=3~9mol%；For MgO as additive, addition is base
Body (1-x) (Bi0.5Na0.5)0.5Sr0.5TiO3-xKNbO3Quality 5%, for increasing disruptive field intensity.
A kind of wide temperature area temperature stabilizing type ceramic capacitor material preparation method of bismuth-sodium titanate base lead-free, including following step
Suddenly：
Step 1：Prepare pure phase ST, pure phase Bi0.5Na0.5TiO3With pure phase KNbO3It is standby.According to mol ratio 1:1 weighs
SrCO3And TiO2It is mixed to form mixture A；According to mol ratio 1:1:4 weigh Bi2O3, Na2CO3And TiO2It is mixed to form mixture
B；According to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixture C.SrCO3、Bi2O3、Na2CO3、TiO2、Nb2O5With
K2CO3Purity be more than 99.0%.
Step 2：Mixture A, B, C are taken, is 1 according to mass ratio respectively with zirconium oxide ballstone and deionized water:2:(0.7
~1), 1:2:(1.5~2), 1:2:(1~1.2) after mixing, using planetary ball mill 18~24h of ball milling, then in 85 DEG C of drying
14~16h, after briquetting, it is placed in batch-type furnace and is incubated 3~3.5 hours respectively at 1130~1150 DEG C, 845~855 DEG C of insulations 4.5
~5.5 hours, 800~810 DEG C were incubated 2~2.5 hours, form ST powders, Bi respectively0.5Na0.5TiO3Powder and KNbO3Powder,
It is standby；
Step 3：According to stoichiometric equation (1-x) (Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3(x=0.03
~0.09mol), take ST powders, Bi0.5Na0.5TiO3Powder, MgO powders and pure phase KNbO3Powder is well mixed to form full dispensing,
And by full dispensing and zirconium oxide ballstone, deionized water, according to mass ratio 1:(2~2.2):(0.8~1) ball milling 18 is carried out after mixing
~24h, drying, wherein drying obtains drying material as the drying condition in step 2；Wherein MgO purity is 99.0%
More than；
Step 4：By ground 120 mesh sieve of drying material, sieving materials are formed；
Step 5：By the sieving materials that step 4 obtains under 210~220MPa pressure, examination is pressed into by isostatic cool pressing
Sample, and the sample made is placed in using zirconium oxide in the aluminum oxide saggar of backing plate, aluminum oxide saggar then to be placed in into microwave and burnt
It is sintered to obtain sintered specimen in freezing of a furnace, wherein sintering condition is：300 DEG C are warming up to 2 DEG C/min, then with 3 DEG C/min liters
Temperature is incubated 3~4 hours to 500~520 DEG C when being then warming up to 1240~1250 DEG C with 5 DEG C/min；Afterwards, dropped with 3 DEG C/min
Temperature is cooled to 500~520 DEG C to 1000 DEG C, then with 5 DEG C/min, finally cools to room temperature with the furnace；
Step 6：The sintered specimen that polishing, cleaning step five obtain, the sintered specimen tow sides after polishing and cleaning
Uniformly coating silver electrode paste, the sample for coating silver electrode is placed in using zirconium oxide in the aluminum oxide saggar of backing plate, then will
Aluminum oxide saggar is placed in batch-type furnace, and it is wide to obtain bismuth-sodium titanate base lead-free by 15~30min of sintering at a temperature of 550~600 DEG C
Temperature area temperature stabilizing type ceramic capacitor material.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
The wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free of the present invention, its formula is (1-x)
(Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3, wherein x=0.03.
Step 1：Prepare pure phase ST, pure phase Bi0.5Na0.5TiO3With pure phase KNbO3It is standby.According to mol ratio 1:1 weighs
SrCO3And TiO2It is mixed to form mixture A；According to mol ratio 1:1:4 weigh Bi2O3, Na2CO3And TiO2It is mixed to form mixture
B；According to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixture C；SrCO3, Bi2O3, Na2CO3、TiO2、Nb2O5With
K2CO3Purity be more than 99.0%；
Step 2：It is respectively 1 according to mass ratio with zirconium oxide ballstone and deionized water to take mixture A, B, C:2:1、1:2:
2、1:2:After 1.2 mixing, using planetary ball mill ball milling 24h, then after 85 DEG C dry 14h, briquetting, it is placed in batch-type furnace and divides
Be not incubated 3 hours in 1150 DEG C, 850 DEG C are incubated 5 hours, and 800 DEG C are incubated 2.5 hours, formed respectively ST powders,
Bi0.5Na0.5TiO3Powder and KNbO3Powder, it is standby；
Step 3：According to (the Bi of stoichiometric equation 0.970.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-0.03KNbO3, take ST
Powder, Bi0.5Na0.5TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing, and by this full dispensing with aoxidizing
Zirconium ballstone, deionized water, according to mass ratio 1:2:Ball milling 20h, drying are carried out after 1 mixing, obtains drying material；MgO purity is
More than 99.0%；
Step 4：By ground 120 mesh sieve of drying material, sieving materials are formed；
Step 5：By the sieving materials that step 4 obtains under 210MPa pressure, sample is pressed into by isostatic cool pressing, and
The sample made is placed in using zirconium oxide as in the aluminum oxide saggar of backing plate, then aluminum oxide saggar is placed in microwave agglomerating furnace
It is sintered to obtain sintered specimen, wherein sintering condition is：300 DEG C are warming up to 2 DEG C/min, then 500 are warming up to 3 DEG C/min
DEG C, it is incubated 3 hours when being then warming up to 1250 DEG C with 5 DEG C/min；Afterwards, 1000 DEG C are cooled to 3 DEG C/min, then with 5 DEG C/
Min is cooled to 500 DEG C, finally cools to room temperature with the furnace；
Step 6：The sintered specimen that polishing, cleaning step five obtain, the sintered specimen tow sides after polishing and cleaning
Uniformly coating silver electrode paste, the sample for coating silver electrode is placed in using zirconium oxide in the aluminum oxide saggar of backing plate, then will
Aluminum oxide saggar is placed in batch-type furnace, and 15min is sintered at a temperature of 550 DEG C and obtains Bi0.5Na0.5TiO3The unleaded wide warm area temperature of base
Spend stabilization type ceramic capacitor material.
Embodiment 2
The wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free of the present invention, its formula is (1-x)
(Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3, wherein x=0.05.
Step 1：Prepare pure phase ST, pure phase Bi0.5Na0.5TiO3With pure phase KNbO3It is standby.According to mol ratio 1:1 weighs
SrCO3And TiO2It is mixed to form mixture A；According to mol ratio 1:1:4 weigh Bi2O3, Na2CO3And TiO2It is mixed to form mixture
B；According to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixture C；SrCO3, Bi2O3, Na2CO3、TiO2、Nb2O5With
K2CO3Purity be more than 99.0%；
Step 2：It is respectively 1 according to mass ratio with zirconium oxide ballstone and deionized water to take mixture A, B, C:2:0.7、1:
2:1.5、1:2:After 1 mixing, using planetary ball mill ball milling 20h, then after 85 DEG C dry 14h, briquetting, it is placed in batch-type furnace
Be incubated 3.5 hours respectively at 1130 DEG C, 845 DEG C are incubated 5.5 hours, and 810 DEG C are incubated 2 hours, formed respectively ST powders,
Bi0.5Na0.5TiO3Powder and KNbO3Powder, it is standby；
Step 3：According to (the Bi of stoichiometric equation 0.950.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-0.05KNbO3, take ST
Powder, Bi0.5Na0.5TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing, and by this full dispensing with aoxidizing
Zirconium ballstone, deionized water, according to mass ratio 1:2.2:Ball milling 24h, drying are carried out after 0.8 mixing, obtains drying material；MgO's is pure
Spend for more than 99.0%；
Step 4：By ground 120 mesh sieve of drying material, sieving materials are formed；
Step 5：By the sieving materials that step 4 obtains under 210MPa pressure, sample is pressed into by isostatic cool pressing, and
The sample made is placed in using zirconium oxide as in the aluminum oxide saggar of backing plate, then aluminum oxide saggar is placed in microwave agglomerating furnace
It is sintered to obtain sintered specimen, wherein sintering condition is：300 DEG C are warming up to 2 DEG C/min, then 520 are warming up to 3 DEG C/min
DEG C, it is incubated 3.5 hours when being then warming up to 1240 DEG C with 5 DEG C/min；Afterwards, 1000 DEG C are cooled to 3 DEG C/min, then with 5 DEG C/
Min is cooled to 520 DEG C, finally cools to room temperature with the furnace；；
Step 6：The sintered specimen that polishing, cleaning step five obtain, the sintered specimen tow sides after polishing and cleaning
Uniformly coating silver electrode paste, the sample for coating silver electrode is placed in using zirconium oxide in the aluminum oxide saggar of backing plate, then will
Aluminum oxide saggar is placed in batch-type furnace, and it is steady to obtain the wide warm area temperature of bismuth-sodium titanate base lead-free by sintering 30min at a temperature of 600 DEG C
Sizing ceramic capacitor material.
Embodiment 3
The wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free of the present invention, its formula is (1-x)
(Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3, wherein x=0.07.
Step 1：Prepare pure phase ST, pure phase Bi0.5Na0.5TiO3With pure phase KNbO3It is standby.According to mol ratio 1:1 weighs
SrCO3And TiO2It is mixed to form mixture A；According to mol ratio 1:1:4 weigh Bi2O3, Na2CO3And TiO2It is mixed to form mixture
B；According to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixture C；SrCO3, Bi2O3, Na2CO3、TiO2、Nb2O5With
K2CO3Purity be more than 99.0%；
Step 2：It is respectively 1 according to mass ratio with zirconium oxide ballstone and deionized water to take mixture A, B, C:2:0.9、1:
2:1.7、1:2:After 1.1 mixing, using planetary ball mill ball milling 18h, then after 85 DEG C dry 15h, briquetting, batch-type furnace is placed in
In respectively at 1140 DEG C be incubated 3.2 hours, 855 DEG C are incubated 4.5 hours, and 805 DEG C are incubated 2.2 hours, formed respectively ST powders,
Bi0.5Na0.5TiO3Powder and KNbO3Powder, it is standby；
Step 3：According to (the Bi of stoichiometric equation 0.930.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-0.07KNbO3, take ST
Powder, Bi0.5Na0.5TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing, and by this full dispensing with aoxidizing
Zirconium ballstone, deionized water, according to mass ratio 1:2.1:Ball milling 22h, drying are carried out after 0.9 mixing, obtains drying material；MgO's is pure
Spend for more than 99.0%；
Step 4：By ground 120 mesh sieve of drying material, sieving materials are formed；
Step 5：By the sieving materials that step 4 obtains under 220MPa pressure, sample is pressed into by isostatic cool pressing, and
The sample made is placed in using zirconium oxide as in the aluminum oxide saggar of backing plate, then aluminum oxide saggar is placed in microwave agglomerating furnace
It is sintered to obtain sintered specimen, wherein sintering condition is：300 DEG C are warming up to 2 DEG C/min, then 500 are warming up to 3 DEG C/min
DEG C, it is incubated 4 hours when being then warming up to 1240 DEG C with 5 DEG C/min；Afterwards, 1000 DEG C are cooled to 3 DEG C/min, then with 5 DEG C/
Min is cooled to 500 DEG C, finally cools to room temperature with the furnace；
Step 6：The sintered specimen that polishing, cleaning step five obtain, the sintered specimen tow sides after polishing and cleaning
Uniformly coating silver electrode paste, the sample for coating silver electrode is placed in using zirconium oxide in the aluminum oxide saggar of backing plate, then will
Aluminum oxide saggar is placed in batch-type furnace, and 15min is sintered at a temperature of 550 DEG C and obtains Bi0.5Na0.5TiO3The unleaded wide warm area temperature of base
Spend stabilization type ceramic capacitor material.
Embodiment 4
The wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free of the present invention, its formula is (1-x)
(Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3, wherein x=0.09.
Step 1：Prepare pure phase ST, pure phase Bi0.5Na0.5TiO3With pure phase KNbO3It is standby.According to mol ratio 1:1 weighs
SrCO3And TiO2It is mixed to form mixture A；According to mol ratio 1:1:4 weigh Bi2O3, Na2CO3And TiO2It is mixed to form mixture
B；According to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixture C；SrCO3, Bi2O3, Na2CO3、TiO2、Nb2O5With
K2CO3Purity be more than 99.0%；
Step 2：It is respectively 1 according to mass ratio with zirconium oxide ballstone and deionized water to take mixture A, B, C:2:1、1:2:
2、1:2:After 1.2 mixing, using planetary ball mill ball milling 24h, then after 85 DEG C dry 16h, briquetting, it is placed in batch-type furnace and divides
3 hours are not incubated in 1150 DEG C, 850 DEG C are incubated 5 hours, and 800 DEG C are incubated 2 hours, form ST powders, Bi respectively0.5Na0.5TiO3
Powder and KNbO3Powder, it is standby；
Step 3：According to (the Bi of stoichiometric equation 0.910.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-0.09KNbO3, take ST
Powder, Bi0.5Na0.5TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing, and by this full dispensing with aoxidizing
Zirconium ballstone, deionized water, according to mass ratio 1:2:Ball milling 18h, drying are carried out after 1 mixing, obtains drying material；MgO purity is
More than 99.0%；
Step 4：By ground 120 mesh sieve of drying material, sieving materials are formed；
Step 5：By the sieving materials that step 4 obtains under 215MPa pressure, sample is pressed into by isostatic cool pressing, and
The sample made is placed in using zirconium oxide as in the aluminum oxide saggar of backing plate, then aluminum oxide saggar is placed in microwave agglomerating furnace
It is sintered to obtain sintered specimen, wherein sintering condition is：300 DEG C are warming up to 2 DEG C/min, then 510 are warming up to 3 DEG C/min
DEG C, it is incubated 3 hours when being then warming up to 1245 DEG C with 5 DEG C/min；Afterwards, 1000 DEG C are cooled to 3 DEG C/min, then with 5 DEG C/
Min is cooled to 510 DEG C, finally cools to room temperature with the furnace；
Step 6：The sintered specimen that polishing, cleaning step five obtain, the sintered specimen tow sides after polishing and cleaning
Uniformly coating silver electrode paste, the sample for coating silver electrode is placed in using zirconium oxide in the aluminum oxide saggar of backing plate, then will
Aluminum oxide saggar is placed in batch-type furnace, and it is steady to obtain the wide warm area temperature of bismuth-sodium titanate base lead-free by sintering 20min at a temperature of 580 DEG C
Sizing ceramic capacitor material.
It will be seen from figure 1 that the ceramic capacitor material prepared by example 1 to example 4, the System forming Ca-Ti ore type
Solid solution ceramic, pseudo- cubic structure is presented, and has MgO and Mg2TiO4Second phase produces.Mg2TiO4Formation be primarily due to
The MgO of addition reacts with matrix.It is can be seen that from Fig. 2 to Fig. 5 with KNbO3The change of doping, all ceramics samples
Equal frequency of occurrences dispersion phenomenon.Figure it is seen that as x=0.03, two abnormal Dielectrics are correspond to 100 DEG C at -50 DEG C
Point, similar phenomenon also appear in Bi0.5Na0.5TiO3In base ceramics, this phenomenon is relevant with relaxation, unrelated with phase transformation.It
Appearance correspond to two distinct types of nanometer polarization microcell (PNRs), be low temperature-PNRs (LT-PNRs) and high temperature PNRs respectively
(HT-PNRs).First abnormal Dielectric point mainly due to caused by LT-PNRs relaxation, second abnormal Dielectric point be by
Phase transformation between two kinds of PNRs is related to HT-PNRs hot differentiation.With KNbO3The increase of doping concentration, it can be seen that be situated between
Electric curve is flattened, and two kinds of PNRs, which are also received, significantly to be influenceed.In order to further go to study the PNRs effect being disturbed, from
The position that Fig. 6 can be seen that first abnormal Dielectric point is little by little moved with x increase to low temperature direction, but dielectric is normal
Several sizes does not change significantly.In view of first abnormal Dielectric point is mainly influenceed by LT-PNRs differentiation, first
The weak reduction for showing LT-PNRs density of abnormal Dielectric point.In addition, dielectric constant corresponding to second abnormal Dielectric point
Have and significantly decline, and the amplitude for being moved to low temperature is more notable.This changes mainly due to the polarization structure of thermal induction
In second abnormal Dielectric point by defect and the chaotic suppression of composition.With x increase, second abnormal Dielectric phenomenon becomes more next
More unobvious, as x=0.09, second abnormal Dielectric peak is barely perceivable, and this is due to KNbO3Doping concentration
Increase, finally change LT-PNRs and HT-PNRs volume ratio.From figure 7 it can be seen that temperature stabilization characteristic is with KNbO3's
Doping is significantly influenceed, and especially in high temperature section, is embodied in the curve for the warm collection of illustrative plates high temperature flatwise that is situated between.Work as x=
During 0.03 and x=0.05, meet X9R characteristics, i.e., when temperature range is -55~200 DEG C, temperature coefficient of capacitance is ± 15%.Especially
Ground, as x=0.03, for sample on the basis of X9R characteristics are met, high temperature section can be extended to 300 DEG C, remain at ± 15% change
In the range of rate, meanwhile, dielectric constant values are maintained at higher level (~1500).As x=0.07 and x=0.09, symbol
X8R characteristics are closed, i.e., when temperature range is -55~150 DEG C, temperature coefficient of capacitance is ± 15%.This four groups of samples are different degrees of
Meet the standard of temperature-stable, it is green suitable for different conditions, there is excellent development potentiality.
Claims (10)
- A kind of 1. wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free, it is characterised in that described metatitanic acid The stoichiometric equation of the unleaded wide temperature area temperature stabilizing type ceramic capacitor material of bismuth sodium base is (1-x) (Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3, wherein x=0.03~0.09.
- A kind of 2. preparation method of the wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free, it is characterised in that Comprise the following steps：Step 1：According to stoichiometric equation (1-x) (Bi0.5Na0.5)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3, x=0.03~ 0.09, take SrTiO3Powder, Bi0.5Na0.5TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing；Step 2：The full dispensing that step 1 is obtained carries out ball milling, drying, sieving, obtains sieving materials；Step 3：The sieving materials that step 2 is obtained are compressing, are then incubated 3~4 hours at 1240~1250 DEG C, sinter To sintered specimen；Step 4：Silver electrode paste is uniformly coated in the sintered specimen tow sides that step 3 obtains, then is sintered to obtain titanium The sour unleaded wide temperature area temperature stabilizing type ceramic capacitor material of bismuth sodium base.
- A kind of 3. system of the wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free according to claim 2 Preparation Method, it is characterised in that SrTiO in step 13The preparation process of powder includes：It is first according to mol ratio 1:1 weighs SrCO3 And TiO2It is mixed to form mixture A；Then mixture A, zirconium oxide ballstone and deionized water are taken, is 1 according to mass ratio:2:(0.7 ~1) ball milling, drying and briquetting are carried out successively after mixing, and are most incubated 3~3.5 hours after 1130~1150 DEG C, are obtained pure phase SrTiO3Powder.
- A kind of 4. system of the wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free according to claim 2 Preparation Method, it is characterised in that Bi in step 10.5Na0.5TiO3The preparation process of powder includes：It is first according to mol ratio 1:1:4 Weigh Bi2O3、Na2CO3And TiO2It is mixed to form mixture B；Then mixture B, zirconium oxide ballstone and deionized water are taken, according to matter Amount is than being 1:2:(1.5~2) ball milling, drying and briquetting are carried out successively after mixing, and are most incubated 4.5~5.5 after 845~855 DEG C Hour, obtain the Bi of pure phase0.5Na0.5TiO3Powder.
- A kind of 5. system of the wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free according to claim 2 Preparation Method, it is characterised in that KNbO in step 13The preparation process of powder includes：It is first according to mol ratio 1:1 weighs Nb2O5With K2CO3It is mixed to form mixture C；Then mixture C, zirconium oxide ballstone and deionized water are taken, is 1 according to mass ratio:2:(1~ 1.2) ball milling, drying and briquetting are carried out successively after mixing, and are most incubated 2~2.5 hours after 800~810 DEG C, are obtained pure phase KNbO3Powder.
- A kind of 6. system of the wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free according to claim 2 Preparation Method, it is characterised in that by full dispensing and zirconium oxide ballstone, deionized water in step 2, according to mass ratio 1:(2~2.2): (0.8~1) ball milling is carried out after mixing.
- A kind of 7. system of the wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free according to claim 2 Preparation Method, it is characterised in that the Ball-milling Time in step 2 is 18~24h.
- A kind of 8. system of the wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free according to claim 2 Preparation Method, it is characterised in that it is 120 mesh that grit number is crossed in step 2.
- A kind of 9. system of the wide temperature area temperature stabilizing type ceramic capacitor material of bismuth-sodium titanate base lead-free according to claim 2 Preparation Method, it is characterised in that sieving materials are compressing by isostatic cool pressing under 210~220MPa pressure in step 3, burn Knot condition is：300 DEG C are warming up to 2 DEG C/min first, then 500~520 DEG C are warming up to 3 DEG C/min, then with 5 DEG C/min liters Temperature is incubated 3~4 hours at 1240~1250 DEG C；Afterwards, 1000 DEG C are cooled to 3 DEG C/min, then are cooled to 5 DEG C/min 500~520 DEG C, finally cool to room temperature with the furnace.
- 10. the wide temperature area temperature stabilizing type ceramic capacitor material of a kind of bismuth-sodium titanate base lead-free according to claim 2 Preparation method, it is characterised in that the sintering condition in step 4 is：15~30min is sintered at a temperature of 550~600 DEG C.
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| CN108585837A (en) * | 2018-05-25 | 2018-09-28 | 西安理工大学 | A kind of preparation method of bismuth-sodium titanate base high temperature capacitors media ceramic |
| CN109574656A (en) * | 2018-12-14 | 2019-04-05 | 武汉理工大学 | A kind of high energy storage bismuth-sodium titanate-strontium titanate base dielectric material and preparation method thereof |
| CN110436920A (en) * | 2019-08-26 | 2019-11-12 | 中南大学 | A kind of bismuth-sodium titanate-sodium tantalate solution ceramic material and its preparation method and application |
| CN112174664A (en) * | 2020-10-11 | 2021-01-05 | 桂林理工大学 | Novel high-energy-storage and high-efficiency sodium niobate-based ceramic material and preparation method thereof |
| CN113735578A (en) * | 2021-09-14 | 2021-12-03 | 陕西师范大学 | Sodium bismuth titanate based lead-free ferroelectric ceramic material with high dielectric temperature stability and energy storage characteristic and preparation method thereof |
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| CN108585837A (en) * | 2018-05-25 | 2018-09-28 | 西安理工大学 | A kind of preparation method of bismuth-sodium titanate base high temperature capacitors media ceramic |
| CN108585837B (en) * | 2018-05-25 | 2021-04-02 | 西安理工大学 | Preparation method of sodium bismuth titanate-based high-temperature capacitor dielectric ceramic |
| CN109574656A (en) * | 2018-12-14 | 2019-04-05 | 武汉理工大学 | A kind of high energy storage bismuth-sodium titanate-strontium titanate base dielectric material and preparation method thereof |
| CN110436920A (en) * | 2019-08-26 | 2019-11-12 | 中南大学 | A kind of bismuth-sodium titanate-sodium tantalate solution ceramic material and its preparation method and application |
| CN110436920B (en) * | 2019-08-26 | 2020-06-16 | 中南大学 | Sodium bismuth titanate-sodium tantalate solid-solution ceramic material and preparation method and application thereof |
| CN112174664A (en) * | 2020-10-11 | 2021-01-05 | 桂林理工大学 | Novel high-energy-storage and high-efficiency sodium niobate-based ceramic material and preparation method thereof |
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| CN113735578B (en) * | 2021-09-14 | 2023-01-17 | 陕西师范大学 | Sodium bismuth titanate based lead-free ferroelectric ceramic material with high dielectric temperature stability and energy storage characteristic and preparation method thereof |
| CN116768617A (en) * | 2023-06-14 | 2023-09-19 | 吉林大学 | Rare earth modified sodium bismuth titanate based capacitor energy storage material and preparation method thereof |
| CN116768617B (en) * | 2023-06-14 | 2024-04-16 | 吉林大学 | Rare earth modified sodium bismuth titanate based capacitor energy storage material and preparation method thereof |
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