CN103011805B - BaTiO3 based leadless X8R type ceramic capacitor dielectric material and preparation method thereof - Google Patents

BaTiO3 based leadless X8R type ceramic capacitor dielectric material and preparation method thereof Download PDF

Info

Publication number
CN103011805B
CN103011805B CN201210566894.1A CN201210566894A CN103011805B CN 103011805 B CN103011805 B CN 103011805B CN 201210566894 A CN201210566894 A CN 201210566894A CN 103011805 B CN103011805 B CN 103011805B
Authority
CN
China
Prior art keywords
batio
tio
ceramic capacitor
dielectric material
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201210566894.1A
Other languages
Chinese (zh)
Other versions
CN103011805A (en
Inventor
蒲永平
高攀
李品
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JIANGSU SUR LIGHTING CO LTD
Shenzhen Pengbo Information Technology Co ltd
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201210566894.1A priority Critical patent/CN103011805B/en
Publication of CN103011805A publication Critical patent/CN103011805A/en
Application granted granted Critical
Publication of CN103011805B publication Critical patent/CN103011805B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention provides a BaTiO3 based leadless X8R type ceramic capacitor dielectric material and a preparation method thereof. The ceramic capacitor dielectric material comprises a main component of BaTiO3 and assistant components of Bi0.5K0.5TiO3 and BaNb206. The preparation method of the dielectric material comprises the steps that BaTiO3 and Bi0.5TiO3 are weighed at a ratio of 9:1, mixed with a zirconium ball stone and deionized water, and subjected to ball milling, drying, briquetting and clinker in sequence to synthesize main crystalline phase Ba0.9(Bi0.5K0.5)0.1TiO3; Ba0.9(Bi0.5K0.5)0.1TiO3 and BaNb2O6 are mixed, subjected to the ball milling, the drying, granulation and sieving at sequence and pressed into a sample; the sample is subjected to heat preservation in 1220-1250 DEG C in air for 3h and then sintered; the molar ratio of the use amount is (1-x)Ba0.9(Bi0.5K0.5)0.1TiO3+xBaNb2O6; x is 0.01-0.04; and the sample is subjected to furnace cooling and finally coated with electrode slurry. The leadless dielectric material prepared with the method has an obvious diffused phase change characteristic and a temperature characteristic of X8R, and is simple in preparation process, low in cost and environment-friendly.

Description

A kind of BaTiO 3base lead-free X 8 R type ceramic capacitor dielectric material and preparation method thereof
[technical field]
The present invention relates to ceramic capacitor dielectric material field, particularly X8R type ceramic capacitor dielectric material and the preparation method of a kind of environmental protection, temperature-stable.
[background technology]
Along with the develop rapidly of information technology and electronic science and technology, electronics is proposed to higher service requirements, for example lightness, chip type and miniaturization, laminated ceramic capacitor (MLCC) is just because these reasons are arisen at the historic moment.At present, the dielectric material of preparing laminated ceramic capacitor that we commonly use is BaTiO 3base pottery.Barium titanate specific inductivity at room temperature can reach 1500～3000, can environment not produced and be polluted simultaneously in production and application process, is therefore well suited for for dielectric materials.But, BaTiO 3curie temperature be about 120 ℃, during higher than Curie temperature, specific inductivity sharply declines, dielectric loss is large, has influence on the temperature stability of ceramic condenser, therefore, must carry out doping vario-property to barium titanate.Barium titanate based ceramic material after suitable doping vario-property has high-k, the feature that low-loss and thermal expansivity are little.
In recent years, laminated ceramic capacitor has started progressively to enter automotive electronics Application Areas, such as control unit of engine (ECU), ABS (Anti-lock Braking System) (ABS), fuel injection program control module (PGMFI) etc., use temperature can reach+and 150 ℃, meet such environment for use, need to tolerate multiple high temp operation and a large amount of thermal shocking.But the capacitance-temperature characteristic of barium phthalate base material has certain limitation, when temperature exceedes 120 ℃, its temperature coefficient of capacitance (△ C/C 20 ℃) exceed 15%, stable dielectric properties cannot be provided.Have EIA (Electronic Industries Association, EIA) X7R characteristic (55 ℃～+ 125 ℃, △ C/C 20 ℃≤ ± 15%, wherein △ C is the electrical capacity C during with 20 ℃ 20 ℃for the electrical capacity C of other temperature spots of benchmark changes △ C=C-C 20 ℃) MLCC be difficult to meet the job requirement under above-mentioned hot conditions.Therefore, develop EIA X8R standard (55 ℃～+ 150 ℃, △ C/C 20 ℃≤ ± 15%) MLCC has received general concern.
Although, BaTiO 3base lead-free X 8 R type ceramic capacitor dielectric material has obtained extensive concern, still, and by Bi 0.5k 0.5tiO 3and BaNb 2o 6codoped BaTiO 3the X8R type ceramic capacitor dielectric material that obtains temperature-stable also rarely has report.Given this, be necessary to provide in fact a kind of BaTiO that can address the above problem 3basic ring is protected X8R type ceramic capacitor material and preparation method.
[summary of the invention]
The object of the invention is to be to provide a kind of BaTiO 3base lead-free X 8 R type ceramic capacitor dielectric material and preparation method thereof, the X8R type ceramic capacitor material making by the inventive method, not only preparation technology is simple, the cost of material is low, and there is, good temperature stability large compared with high specific inductivity, low dielectric loss, body resistivity, likely become and substitute lead base stupalith and become the laminated ceramic capacitor excellent important candidate material of holding concurrently technically and economically.
For achieving the above object, the present invention takes following technical scheme:
A kind of BaTiO 3the preparation method of base lead-free X 8 R type ceramic capacitor dielectric material, comprises the steps:
Step 1: preparation BaTiO 3, Bi 0.5k 0.5tiO 3and BaNb 2o 6standby; According to mol ratio, 1:1 takes BaCO 3and TiO 2be mixed to form mixture A; According to mol ratio, 1:1:4 takes Bi 2o 3, K 2cO 3and TiO 2be mixed to form mixture B; According to mol ratio, 1:1 takes BaCO 3and Nb 2o 5be mixed to form mixture C;
Step 2: get mixture A, B, C, respectively with zirconium ballstone and deionized water, according to mass ratio, be to carry out successively after ball milling, oven dry, briquetting after 1:1:1 mixes, be placed in retort furnace respectively at 1150 ℃ of insulations 2 hours, 950 ℃ are incubated 3 hours, 1000 ℃ are incubated 2 hours, form respectively the BaTiO of pure phase 3, Bi 0.5k 0.5tiO 3and BaNb 2o 6powder, standby;
Step 3: with pure phase BaTiO 3ratio is 90mol%, pure phase Bi 0.5k 0.5tiO 3ratio is for being 10mol% meter, after mixing, form mixture D, getting mixture D and zirconium ballstone and deionized water, is 1:1 according to mass ratio: after 1 mixing, carry out successively after ball milling, oven dry, briquetting, be placed in retort furnace and form principal crystalline phase Ba in 1100 ℃ of insulations pre-burning in 2 hours 0.9(Bi 0.5k 0.5) 0.1tiO 3powder, standby;
Step 4: with principal crystalline phase Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3with pure phase BaNb 2o 6powder is 1mol meter altogether, according to molar content, takes 1～4mol%BaNb 2o 6powder, is added into Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3middle formation is prepared burden entirely;
Step 5: getting respectively full batching and zirconium ballstone and deionized water that step 4 obtains, is to carry out successively ball milling, oven dry, granulation, sieve after 1:1:1 mixes according to mass ratio, forms granulation material;
Step 6: step 5 gained granulation material is made to sample under the pressure of 120MPa, then, be placed in the inherent high temperature box furnace of aluminum oxide saggar take zirconium white as backing plate, with 2 ℃/min, be warming up to 500 ℃ of insulation 60min, while being warming up to 1220～1250 ℃ with 5 ℃/min, be incubated 3 hours, afterwards, with 5 ℃/min, be cooled to after 500 ℃, cool to room temperature with the furnace;
Step 7: after polishing, the sample that sinters of cleaning step six, evenly apply silver electrode paste at sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO 3base X8R type ceramic capacitor material sample.
As the preferred embodiment of the invention, in step 5, Ball-milling Time is 4 hours.
As the preferred embodiment of the invention, in step 5, after full batching, zirconium ballstone and deionized water mixing, ball milling, oven dry, form and dry material, the tackiness agent that is 4～6% by mass concentration is added into and wherein carries out granulation, tackiness agent accounts for dries 8～10% of material quality, crosses respectively 40 orders and 80 mesh sieves and gets middle material.
As the preferred embodiment of the invention, described tackiness agent is polyvinyl alcohol water solution.
As the preferred embodiment of the invention, the BaNb taking according to molar content in step 4 2o 6powder amount is 1mol%, 2mol%, 3mol% and 4mol%.
BaTiO prepared by the inventive method 3base lead-free X 8 R type ceramic capacitor dielectric material, major ingredient is BaTiO 3and Bi 0.5k 0.5tiO 3, its mol ratio is 9:1, the synthetic principal crystalline phase of pre-burning after mixing, and auxiliary material is BaNb 2o 6; Major ingredient and auxiliary material are mixed to form full batching; Wherein, according to molar percentage meter, BaNb 2o 6account for 1～4mol% of full batching.
BaTiO prepared by the inventive method 3base lead-free X 8 R type ceramic capacitor dielectric material, its formula is (1-x) Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3+ xBaNb 2o 6, wherein x=0.01～0.04, x is molar percentage.
A kind of BaTiO 3base lead-free X 8 R type ceramic capacitor dielectric material, its formula is (1-x) Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3+ xBaNb 2o 6, wherein x=0.01～0.04, x is molar percentage.
As the preferred embodiment of the invention, x=0.01,0.02,0.03 or 0.04.
BaTiO of the present invention 3base lead-free X 8 R type ceramic capacitor dielectric material and preparation method thereof, at least has the following advantages: 1. adopt conventional solid-state method preparation, technical maturity, is applicable to industrialization and produces.2. adopt Bi 0.5k 0.5tiO 3and BaNb 2o 6carry out codoped, realize the disperse phase transformation that electricity price compensation is conducive to realize barium titanate ceramics.3. not only preparation technology is simple for the lead-free X 8 R type ceramic capacitor dielectric material that prepared by the inventive method, the cost of material is low, and have compared with high specific inductivity, low dielectric loss, body resistivity is large, temperature stability good, to substituting lead base stupalith, becomes the laminated ceramic capacitor excellent important candidate material of holding concurrently technically and economically.
[accompanying drawing explanation]
Fig. 1 is the rational curve that the dielectric constant with temperature of embodiment 1 sample changes;
Fig. 2 is the temperature variant rational curve of temperature coefficient of capacitance of embodiment 1 sample;
Fig. 3 is the rational curve that the dielectric constant with temperature of embodiment 2 samples changes;
Fig. 4 is the temperature variant rational curve of temperature coefficient of capacitance of embodiment 2 samples;
Fig. 5 is the rational curve that the dielectric constant with temperature of embodiment 3 samples changes;
Fig. 6 is the temperature variant rational curve of temperature coefficient of capacitance of embodiment 3 samples;
Fig. 7 is the rational curve that the dielectric constant with temperature of embodiment 4 samples changes;
Fig. 8 is the temperature variant rational curve of temperature coefficient of capacitance of embodiment 4 samples;
[embodiment]
BaTiO of the present invention 3the preparation method of base lead-free X 8 R type ceramic capacitor dielectric material, specific as follows:
Embodiment 1:
BaTiO of the present invention 3basic ring is protected temperature-stable X8R type ceramic capacitor dielectric material, and its formula is (1-x) Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3+ xBaNb 2o 6, wherein x=0.01(molar percentage).
Step 1: preparation BaTiO 3, Bi 0.5k 0.5tiO 3and BaNb 2o 6standby.According to mol ratio, 1:1 takes BaCO 3and TiO 2be mixed to form mixture A; According to mol ratio, 1:1:4 takes Bi 2o 3, K 2cO 3and TiO 2be mixed to form mixture B; According to mol ratio, 1:1 takes BaCO 3and Nb 2o 5be mixed to form mixture C.
Step 2: get mixture A, B, C, respectively with zirconium ballstone and deionized water, according to mass ratio, be 1:1: after 1 mixing, carry out successively after ball milling, oven dry, briquetting, be placed in retort furnace respectively at 1150 ℃ of insulations 2 hours, 950 ℃ are incubated 3 hours, 1000 ℃ are incubated 2 hours, form respectively the BaTiO of pure phase 3, Bi 0.5k 0.5tiO 3and BaNb 2o 6powder, standby;
Step 3: with pure phase BaTiO 3ratio is 90mol%, pure phase Bi 0.5k 0.5tiO 3ratio is 10mol% meter, after mixing, forms mixture D, gets mixture D and zirconium ballstone and deionized water, is 1: 1:1 carries out after ball milling, oven dry, briquetting after mixing successively according to mass ratio, is placed in retort furnace and forms principal crystalline phase Ba in 1100 ℃ of insulations pre-burning in 2 hours 0.9(Bi 0.5k 0.5) 0.1tiO 3powder, standby;
Step 4: with principal crystalline phase Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3with pure phase BaNb 2o 6powder is 1mol meter altogether, according to molar content, takes 1mol%BaNb 2o 6powder, is added into Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3middle formation is prepared burden entirely;
Step 5: getting respectively full batching and zirconium ballstone and deionized water that step 4 obtains, is to carry out successively ball milling, oven dry, granulation, sieve after 1:1:1 mixes according to mass ratio, forms granulation material;
Step 6: step 5 gained granulation material is made to sample under the pressure of 120MPa, then, be placed in the inherent high temperature box furnace of aluminum oxide saggar take zirconium white as backing plate, with 2 ℃/min, be warming up to 500 ℃ of insulation 60min, while being warming up to 1250 ℃ with 5 ℃/min, be incubated 3 hours, afterwards, with 5 ℃/min, be cooled to after 500 ℃, cool to room temperature with the furnace;
Step 7: after polishing, the sample that sinters of cleaning step six, evenly apply silver electrode paste at sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO 3base lead-free X 8 R type ceramic capacitor material sample.
Embodiment 2:
BaTiO of the present invention 3basic ring is protected temperature-stable X8R type ceramic capacitor dielectric material, and its formula is (1-x) Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3+ xBaNb 2o 6, wherein x=0.02(molar percentage);
Step 1: preparation BaTiO 3, Bi 0.5k 0.5tiO 3and BaNb 2o 6standby.According to mol ratio, 1:1 takes BaCO 3and TiO 2be mixed to form mixture A; According to mol ratio, 1:1:4 takes Bi 2o 3, K 2cO 3and TiO 2be mixed to form mixture B; According to mol ratio, 1:1 takes BaCO 3and Nb 2o 5be mixed to form mixture C.
Step 2: get mixture A, B, C, respectively with zirconium ballstone and deionized water, according to mass ratio, be to carry out successively after ball milling, oven dry, briquetting after 1:1:1 mixes, be placed in retort furnace respectively at 1150 ℃ of insulations 2 hours, 950 ℃ are incubated 3 hours, 1000 ℃ are incubated 2 hours, form respectively the BaTiO of pure phase 3, Bi 0.5k 0.5tiO 3and BaNb 2o 6powder, standby;
Step 3: with pure phase BaTiO 3ratio is 90mol%, pure phase Bi 0.5k 0.5tiO 3ratio is 10%mol meter, after mixing, forms mixture D, gets mixture D and zirconium ballstone and deionized water, according to mass ratio, is to carry out successively after ball milling, oven dry, briquetting after 1:1:1 mixes, and is placed in retort furnace and forms principal crystalline phase Ba in 1100 ℃ of insulations pre-burning in 2 hours 0.9(Bi 0.5k 0.5) 0.1tiO 3powder, standby;
Step 4: with principal crystalline phase Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3with pure phase BaNb 2o 6powder is 1mol meter altogether, according to molar content, takes 2mol%BaNb 2o 6powder, is added into Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3middle formation is prepared burden entirely;
Step 5: getting respectively full batching and zirconium ballstone and deionized water that step 4 obtains, is 1 according to mass ratio: 1:1 carries out successively ball milling, oven dry, granulation after mixing, sieves, and forms granulation material;
Step 6: step 5 gained granulation material is made to sample under the pressure of 120MPa, then, be placed in the inherent high temperature box furnace of aluminum oxide saggar take zirconium white as backing plate, with 2 ℃/min, be warming up to 500 ℃ of insulation 60min, while being warming up to 1240 ℃ with 5 ℃/min, be incubated 3 hours, afterwards, with 5 ℃/min, be cooled to after 500 ℃, cool to room temperature with the furnace;
Step 7: after polishing, the sample that sinters of cleaning step six, evenly apply silver electrode paste at sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO 3base lead-free X 8 R type ceramic capacitor material sample.
Embodiment 3:
BaTiO of the present invention 3basic ring is protected temperature-stable X8R type ceramic capacitor dielectric material, and its formula is (1-x) Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3+ xBaNb 2o 6, wherein x=0.03(molar percentage);
Step 1: preparation BaTiO 3, Bi 0.5k 0.5tiO 3and BaNb 2o 6standby.According to mol ratio, 1:1 takes BaCO 3and TiO 2be mixed to form mixture A; According to mol ratio, 1:1:4 takes Bi 2o 3, K 2cO 3and TiO 2be mixed to form mixture B; According to mol ratio, 1:1 takes BaCO 3and Nb 2o 5be mixed to form mixture C.
Step 2: get mixture A, B, C, respectively with zirconium ballstone and deionized water, according to mass ratio, be to carry out successively after ball milling, oven dry, briquetting after 1:1:1 mixes, be placed in retort furnace respectively at 1150 ℃ of insulations 2 hours, 950 ℃ are incubated 3 hours, 1000 ℃ are incubated 2 hours, form respectively the BaTiO of pure phase 3, Bi 0.5k 0.5tiO 3and BaNb 2o 6powder, standby;
Step 3: with pure phase BaTiO 3ratio is 90mol%, pure phase Bi 0.5k 0.5tiO 3ratio is 10%mol meter, after mixing, forms mixture D, gets mixture D and zirconium ballstone and deionized water, according to mass ratio, is to carry out successively after ball milling, oven dry, briquetting after 1:1:1 mixes, and is placed in retort furnace and forms principal crystalline phase Ba in 1100 ℃ of insulations pre-burning in 2 hours 0.9(Bi 0.5k 0.5) 0.1tiO 3powder, standby;
Step 4: with principal crystalline phase Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3with pure phase BaNb 2o 6powder is 1mol meter altogether, according to molar content, takes 3mol%BaNb 2o 6powder, is added into Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3middle formation is prepared burden entirely;
Step 5: getting respectively full batching and zirconium ballstone and deionized water that step 4 obtains, is 1 according to mass ratio: 1:1 carries out successively ball milling, oven dry, granulation after mixing, sieves, and forms granulation material;
Step 6: step 5 gained granulation material is made to sample under the pressure of 120MPa, then, be placed in the inherent high temperature box furnace of aluminum oxide saggar take zirconium white as backing plate, with 2 ℃/min, be warming up to 500 ℃ of insulation 60min, while being warming up to 1230 ℃ with 5 ℃/min, be incubated 3 hours, afterwards, with 5 ℃/min, be cooled to after 500 ℃, cool to room temperature with the furnace;
Step 7: after polishing, the sample that sinters of cleaning step six, evenly apply silver electrode paste at sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO 3base lead-free X 8 R type ceramic capacitor material sample.
Embodiment 4:
BaTiO of the present invention 3basic ring is protected temperature-stable X8R type ceramic capacitor dielectric material, and its formula is (1-x) Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3+ xBaNb 2o 6, wherein x=0.04(molar percentage);
Step 1: preparation BaTiO 3, Bi 0.5k 0.5tiO 3and BaNb 2o 6standby.According to mol ratio, take BaCO at 1: 1 3and TiO 2be mixed to form mixture A; According to mol ratio, 1:1:4 takes Bi 2o 3, K 2cO 3and TiO 2be mixed to form mixture B; According to mol ratio, 1:1 takes BaCO 3and Nb 2o 5be mixed to form mixture C.
Step 2: get mixture A, B, C, respectively with zirconium ballstone and deionized water, according to mass ratio, be to carry out successively after ball milling, oven dry, briquetting after 1:1:1 mixes, be placed in retort furnace respectively at 1150 ℃ of insulations 2 hours, 950 ℃ are incubated 3 hours, 1000 ℃ are incubated 2 hours, form respectively the BaTiO of pure phase 3, Bi 0.5k 0.5tiO 3and BaNb 2o 6powder, standby;
Step 3: with pure phase BaTiO 3ratio is 90mol%, pure phase Bi 0.5k 0.5tiO 3ratio is 10%mol meter, after mixing, forms mixture D, gets mixture D and zirconium ballstone and deionized water, according to mass ratio, is to carry out successively after ball milling, oven dry, briquetting after 1:1:1 mixes, and is placed in retort furnace and forms principal crystalline phase Ba in 1100 ℃ of insulations pre-burning in 2 hours 0.9(Bi 0.5k 0.5) 0.1tiO 3powder, standby;
Step 4: with principal crystalline phase Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3with pure phase BaNb 2o 6powder is 1mol meter altogether, according to molar content, takes 4mol%BaNb 2o 6powder, is added into Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3middle formation is prepared burden entirely;
Step 5: getting respectively full batching and zirconium ballstone and deionized water that step 4 obtains, is 1 according to mass ratio: 1:1 carries out successively ball milling, oven dry, granulation after mixing, sieves, and forms granulation material;
Step 6: step 5 gained granulation material is made to sample under the pressure of 120MPa, then, be placed in the inherent high temperature box furnace of aluminum oxide saggar take zirconium white as backing plate, with 2 ℃/min, be warming up to 500 ℃ of insulation 60min, while being warming up to 1220 ℃ with 5 ℃/min, be incubated 3 hours, afterwards, with 5 ℃/min, be cooled to after 500 ℃, cool to room temperature with the furnace;
Step 7: after polishing, the sample that sinters of cleaning step six, evenly apply silver electrode paste at sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO 3base lead-free X 8 R type ceramic capacitor material sample.
Refer to shown in Fig. 1 to Fig. 8, dielectric properties tests shows: embodiment 1 to embodiment 4 prepared ceramic medium material all meet EIA X8R standard (55 ℃～+ 150 ℃, △ C/C 20 ℃≤ ± 15%), concrete parameters is as shown in table 1.
The dielectric properties test data (1kHz) of ceramics sample prepared by table 1 embodiment 1-4
Figure BDA00002641128300091
By doping K 0.5bi 0.5tiO 3, and and BaTiO 3form sosoloid, can effectively improve Curie temperature, Curie peak is moved to high temperature direction, can also reduce sintering temperature; Along with BaNb 2o 6the increase of content, can make grain refining, and this is because Nb 5+at BaTiO 3in solid solubility limited, and the diffuser efficiency in crystal grain is extremely low, therefore, if Nb 5+content when more, part can be enriched in crystal boundary, can effectively suppress the growth of crystal grain, makes grain formation stable nucleocapsid structure.Meanwhile, form the fluctuating of micro components, composition fluctuation theory proposes based on compound ion stochastic distribution phenomenon.Think that different ions such as occupies at random at the isomorphous position, produce the different microcell of microscopic concentration and integral macroscopic concentration, form different microcell and there is slightly different Curie temperature, in macroscopic view, produce the transition temperature area of broadening, even if the average component of microcell is identical, also may form because cell configuration is different the different microcell of structure, thereby produce disperse phase transformation.By adulterating or changing the scantlings of the structure of crystal grain, can make the Curie temperature of ferroelectric ceramic(s) change, the specific inductivity of peak value both sides rises, the warm curve that is situated between becomes more extensive, smooth, this by adulterating or changing crystalline-granular texture size and improve the effect of the temperature stability of ceramic dielectric constant, be called broadening effect.The barium titanate-based lead-free X8R type ceramic capacitor dielectric material that the present invention is prepared, not only preparation technology is simple, the cost of material is low, and have compared with high specific inductivity, low dielectric loss, body resistivity is large, temperature stability is good, being expected to substitute lead base stupalith becomes laminated ceramic capacitor one of the excellent important candidate material of holding concurrently technically and economically.

Claims (7)

1. a BaTiO 3the preparation method of base lead-free X 8 R type ceramic capacitor dielectric material, is characterized in that: comprise the steps:
Step 1: preparation BaTiO 3, Bi 0.5k 0.5tiO 3and BaNb 2o 6standby; According to mol ratio, 1:1 takes BaCO 3and TiO 2be mixed to form mixture A; According to mol ratio, 1:1:4 takes Bi 2o 3, K 2cO 3and TiO 2be mixed to form mixture B; According to mol ratio, 1:1 takes BaCO 3and Nb 2o 5be mixed to form mixture C;
Step 2: get mixture A, B, C, respectively with zirconium ballstone and deionized water, according to mass ratio, be to carry out successively after ball milling, oven dry, briquetting after 1:1:1 mixes, be placed in retort furnace respectively at 1150 ℃ of insulations 2 hours, 950 ℃ are incubated 3 hours, 1000 ℃ are incubated 2 hours, form respectively the BaTiO of pure phase 3, Bi 0.5k 0.5tiO 3and BaNb 2o 6powder, standby;
Step 3: with pure phase BaTiO 3ratio is 90mol%, pure phase Bi 0.5k 0.5tiO 3ratio is 10mol% meter, after mixing, forms mixture D, gets mixture D and zirconium ballstone and deionized water, according to mass ratio, is to carry out successively after ball milling, oven dry, briquetting after 1:1:1 mixes, and is placed in retort furnace and forms principal crystalline phase Ba in 1100 ℃ of insulations pre-burning in 2 hours 0.9(Bi 0.5k 0.5) 0.1tiO 3powder, standby;
Step 4: with principal crystalline phase Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3with pure phase BaNb 2o 6powder is 1mol meter altogether, according to molar content, takes 1～4mol%BaNb 2o 6powder, is added into Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3middle formation is prepared burden entirely;
Step 5: getting respectively full batching and zirconium ballstone and deionized water that step 4 obtains, is to carry out successively ball milling, oven dry, granulation, sieve after 1:1:1 mixes according to mass ratio, forms granulation material;
Step 6: step 5 gained granulation material is made to sample under the pressure of 120MPa, then, be placed in the inherent high temperature box furnace of aluminum oxide saggar take zirconium white as backing plate, with 2 ℃/min, be warming up to 500 ℃ of insulation 60min, while being warming up to 1220～1250 ℃ with 5 ℃/min, be incubated 3 hours, afterwards, with 5 ℃/min, be cooled to after 500 ℃, cool to room temperature with the furnace;
Step 7: after polishing, the sample that sinters of cleaning step six, evenly apply silver electrode paste at sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO 3base X8R type ceramic capacitor material sample.
2. BaTiO as claimed in claim 1 3the preparation method of base lead-free X 8 R type ceramic capacitor dielectric material, is characterized in that: in step 5, Ball-milling Time is 4 hours.
3. BaTiO as claimed in claim 1 3the preparation method of base lead-free X 8 R type ceramic capacitor dielectric material, it is characterized in that: in step 5, after full batching, zirconium ballstone and deionized water mixing, ball milling, oven dry, form and dry material, the tackiness agent that is 4～6% by mass concentration is added into and wherein carries out granulation, tackiness agent accounts for dries 8～10% of material quality, crosses respectively 40 orders and 80 mesh sieves and gets middle material.
4. BaTiO as claimed in claim 3 3the preparation method of base lead-free X 8 R type ceramic capacitor dielectric material, is characterized in that: described tackiness agent is polyvinyl alcohol water solution.
5. BaTiO as claimed in claim 1 3the preparation method of base lead-free X 8 R type ceramic capacitor dielectric material, is characterized in that: the amount of the mixture C pre-synthesis material taking according to molar content in step 4 is 1mol%, 2mol%, 3mol% or 4mol%.
6. according to the BaTiO described in any one in claim 1 to 4 3the BaTiO that the preparation method of base lead-free X 8 R type ceramic capacitor dielectric material prepares 3base lead-free X 8 R type ceramic capacitor dielectric material, is characterized in that: major ingredient is BaTiO 3and Bi 0.5k 0.5tiO 3, its mol ratio is 9:1, pre-burning after mixing, and auxiliary material is BaNb 2o 6; Major ingredient and auxiliary material are mixed to form full batching; Wherein, according to molar percentage meter, BaNb 2o 6account for 1～4mol% of full batching.
7. according to BaTiO claimed in claim 1 3the BaTiO that the preparation method of base lead-free X 8 R type ceramic capacitor dielectric material prepares 3base lead-free X 8 R type ceramic capacitor dielectric material, is characterized in that: its formula is (1-x) Ba 0.9(Bi 0.5k 0.5) 0.1tiO 3+ xBaNb 2o 6, wherein x=0.01～0.04, x is molar percentage.
CN201210566894.1A 2012-12-24 2012-12-24 BaTiO3 based leadless X8R type ceramic capacitor dielectric material and preparation method thereof Active CN103011805B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210566894.1A CN103011805B (en) 2012-12-24 2012-12-24 BaTiO3 based leadless X8R type ceramic capacitor dielectric material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210566894.1A CN103011805B (en) 2012-12-24 2012-12-24 BaTiO3 based leadless X8R type ceramic capacitor dielectric material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103011805A CN103011805A (en) 2013-04-03
CN103011805B true CN103011805B (en) 2014-04-16

Family

ID=47960973

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210566894.1A Active CN103011805B (en) 2012-12-24 2012-12-24 BaTiO3 based leadless X8R type ceramic capacitor dielectric material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103011805B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104261819A (en) * 2014-09-16 2015-01-07 陕西科技大学 BaTiO3-based lead-free temperature-stable ceramic capacitor dielectric material and preparation method thereof
CN105236958A (en) * 2015-08-24 2016-01-13 陕西科技大学 X9R type multilayer ceramic capacitor dielectric material and preparation method therefor
CN105236957A (en) * 2015-08-24 2016-01-13 陕西科技大学 Y8R type multilayer ceramic capacitor dielectric material and preparation method therefor
CN106892659A (en) * 2017-03-31 2017-06-27 天津大学 A kind of anti-reduction huge dielectric constant medium material for multilayer ceramic capacitors
CN107399970A (en) * 2017-07-13 2017-11-28 天津大学 A kind of medium material for multilayer ceramic capacitors with superior insulation characteristics
CN110423111B (en) * 2019-07-30 2022-03-25 陕西科技大学 Environment-friendly lead-free ceramic material with high energy storage performance and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6723673B2 (en) * 2000-08-31 2004-04-20 Mra Laboratories, Inc. High dielectric constant very low fired X7R ceramic capacitor, and powder for making
CN102515762A (en) * 2011-12-22 2012-06-27 四川师范大学 Sodium niobate barium-bismuth-potassium titanate lead-free piezoelectric ceramic composition

Also Published As

Publication number Publication date
CN103011805A (en) 2013-04-03

Similar Documents

Publication Publication Date Title
CN103011805B (en) BaTiO3 based leadless X8R type ceramic capacitor dielectric material and preparation method thereof
CN102674832B (en) Barium-titanate-base lead-free bismuth-containing relaxation ferroelectric ceramic material and preparation method thereof
CN101781115B (en) X8R type multilayer ceramic capacitor dielectric material and preparation method thereof
CN101531510A (en) Lead-free capacitor ceramics with stability at high temperature and preparation method thereof
CN110015894B (en) Sodium bismuth titanate-based ceramic with high dielectric stability at high temperature and preparation method and application thereof
CN101570434A (en) X8R type base metal inner electrode multilayer ceramic capacitor dielectric material and preparation method thereof
CN111004030B (en) MgTiO (magnesium-titanium-oxide) powder3Microwave-based dielectric ceramic and preparation method thereof
CN106588006A (en) High-dielectric property BST (Barium Strontium Titanate), preparation method thereof and dielectric ceramic prepared by adopting same
CN108863348A (en) A kind of dielectric ceramic material and preparation method thereof of ultra-wide temperature stability
CN104692797A (en) Barium strontium titanate-based capacitor ceramic and preparation method thereof
CN108585837B (en) Preparation method of sodium bismuth titanate-based high-temperature capacitor dielectric ceramic
CN104030678B (en) A kind of BaTiO 3base unleaded relaxation type ceramic dielectric material and preparation method thereof
CN108863349A (en) A kind of barium titanate-based lead-free height Jie temperature-stable ceramic material and preparation method thereof
CN115385688B (en) Barium strontium zirconate titanate-based dielectric ceramic material and preparation method thereof
CN106045500A (en) Preparation method of NBT-based high-temperature low-loss ceramic capacitor
CN104725036B (en) A kind of barium-strontium titanate-based energy storage ceramic of high temperature low loss and preparation method thereof
CN106145932B (en) A kind of medium material for multilayer ceramic capacitors of high dielectric constant and preparation method thereof
CN103641477B (en) Anti-ferroelectric energy storage ceramic material and preparation method thereof
CN105236958A (en) X9R type multilayer ceramic capacitor dielectric material and preparation method therefor
CN102531592B (en) Reduction-resistant Y5P ceramic capacitor dielectric porcelain
CN105036735A (en) Z7R-type multilayer ceramic capacitor dielectric material and preparation method thereof
CN105384436A (en) Titanium-rich barium strontium titanate-based dielectric medium ceramic material and preparation method thereof
CN102060523B (en) Composite material with high dielectric constant and preparation method thereof
CN110304916A (en) A kind of anti-reduction BaTiO3Base media ceramic and preparation method
CN105130424A (en) BiYO3-doped BaTiO3-based relaxor ferroelectric and preparation method therefor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20201221

Address after: 224000 Yancheng Tinghu District Yandong Town Southeast Industrial Park, Jiangsu Province

Patentee after: JIANGSU SUR LIGHTING Co.,Ltd.

Address before: 518000 No.6 Qinglong Road, Qinglong Road, Qinghua community, Longhua street, Longhua District, Shenzhen City, Guangdong Province

Patentee before: Shenzhen Pengbo Information Technology Co.,Ltd.

Effective date of registration: 20201221

Address after: 518000 No.6 Qinglong Road, Qinglong Road, Qinghua community, Longhua street, Longhua District, Shenzhen City, Guangdong Province

Patentee after: Shenzhen Pengbo Information Technology Co.,Ltd.

Address before: No. 1, Weiyang District university garden, Xi'an, Shaanxi Province, Shaanxi

Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY