CN103011805A - 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

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CN103011805A
CN103011805A CN2012105668941A CN201210566894A CN103011805A CN 103011805 A CN103011805 A CN 103011805A CN 2012105668941 A CN2012105668941 A CN 2012105668941A CN 201210566894 A CN201210566894 A CN 201210566894A CN 103011805 A CN103011805 A CN 103011805A
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ceramic capacitor
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CN103011805B (en
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蒲永平
高攀
李品
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JIANGSU SUR LIGHTING CO LTD
Shenzhen Pengbo Information Technology Co ltd
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Shaanxi University of Science and Technology
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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 the 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 higher service requirements, lightness for example, chip type and miniaturization, laminated ceramic capacitor (MLCC) just arises at the historic moment because of these reasons.At present, our dielectric material of the preparation laminated ceramic capacitor commonly used is BaTiO 3The base pottery.Barium titanate specific inductivity at room temperature can reach 1500～3000, can not produce environment in production and application process simultaneously and pollute, and therefore is well suited for for dielectric materials.Yet, BaTiO 3Curie temperature be about 120 ℃, specific inductivity sharply descends when being higher than Curie temperature, dielectric loss is large, has influence on the temperature stability of ceramic condenser, therefore, must carry out doping vario-property to barium titanate.Has high-k, the characteristics that low-loss and thermal expansivity are little through the barium titanate based ceramic material behind the suitable doping vario-property.
In recent years, laminated ceramic capacitor has begun progressively to enter the 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 ℃, satisfy such environment for use, need the operation of tolerance multiple high temp and a large amount of thermal shocking.Yet the capacitance-temperature characteristic of barium phthalate base material has certain limitation, when temperature surpasses 120 ℃, and its temperature coefficient of capacitance (△ C/C 20 ℃) surpass 15%, stable dielectric properties can't 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 satisfy job requirement under the 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 with 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 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 that makes by the inventive method, not only preparation technology is simple, the cost of material is low, and have that higher specific inductivity, low dielectric loss, body resistivity are large, good temperature stability, might become and substitute the 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 6For subsequent use; 1:1 takes by weighing BaCO according to mol ratio 3And TiO 2Mixed-shaped resulting mixture A; 1:1:4 takes by weighing Bi according to mol ratio 2O 3, K 2CO 3And TiO 2Mixed-shaped resulting mixture B; 1:1 takes by weighing BaCO according to mol ratio 3And Nb 2O 5Mixed-shaped resulting mixture C;
Step 2: get mixture A, B, C, respectively with zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixes after, place 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, for subsequent use;
Step 3: with pure phase BaTiO 3Ratio is 90mol%, pure phase Bi 0.5K 0.5TiO 3Ratio is the 10mol% meter, forms mixture D after mixing, and gets mixture D and zirconium ballstone and deionized water, is 1:1 according to mass ratio: after carrying out ball milling, oven dry, briquetting successively after 1 mixing, place retort furnace to form principal crystalline phase Ba in 1100 ℃ of insulations pre-burning in 2 hours 0.9(Bi 0.5K 0.5) 0.1TiO 3Powder, for subsequent use;
Step 4: with principal crystalline phase Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3With pure phase BaNb 2O 6Powder is the 1mol meter altogether, takes by weighing 1～4mol%BaNb according to molar content 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 after 1:1:1 mixes, sieve according to mass ratio, forms the granulation material;
Step 6: step 5 gained granulation material is made sample under the pressure of 120MPa, then, place in the inherent high temperature box furnace of aluminum oxide saggar take zirconium white as backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 3 hours when being warming up to 1220～1250 ℃ with 5 ℃/min, afterwards, be cooled to 500 ℃ with 5 ℃/min after, cool to room temperature with the furnace;
Step 7: behind polishing, the sample that sinters of cleaning step six, evenly apply silver electrode paste at the 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 the step 5, Ball-milling Time is 4 hours.
As the preferred embodiment of the invention, in the step 5, form the oven dry material after full batching, zirconium ballstone and deionized water mixing, ball milling, the oven dry, be that 4～6% tackiness agent is added into and wherein carries out granulation with mass concentration, tackiness agent accounts for 8～10% of oven dry 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 that takes by weighing according to molar content in the step 4 2O 6The powder amount is 1mol%, 2mol%, 3mol% and 4mol%.
The BaTiO of the inventive method preparation 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 6Major ingredient and auxiliary material mixed-shaped are helped batching; Wherein, according to molar percentage meter, BaNb 2O 6Account for 1～4mol% of full batching.
The BaTiO of the inventive method preparation 3Base lead-free X 8 R type ceramic capacitor dielectric material, its prescription is (1-x) Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3+ xBaNb 2O 6, x=0.01～0.04 wherein, x is molar percentage.
A kind of BaTiO 3Base lead-free X 8 R type ceramic capacitor dielectric material, its prescription is (1-x) Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3+ xBaNb 2O 6, x=0.01～0.04 wherein, 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 has the following advantages at least: 1. adopt the conventional solid-state method preparation, technical maturity is fit to industrialization production.2. adopt Bi 0.5K 0.5TiO 3And BaNb 2O 6Carry out codoped, realize that the electricity price compensation is conducive to realize the disperse phase transformation of barium titanate ceramics.3. not only preparation technology is simple for the lead-free X 8 R type ceramic capacitor dielectric material of the inventive method preparation, the cost of material is low, and have higher specific inductivity, low dielectric loss, body resistivity is large, temperature stability good, becomes the laminated ceramic capacitor excellent important candidate material of holding concurrently technically and economically to substituting the lead base stupalith.
[description of drawings]
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 insulation degree is stablized X8R type ceramic capacitor dielectric material, and its prescription is (1-x) Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3+ xBaNb 2O 6, x=0.01(molar percentage wherein).
Step 1: preparation BaTiO 3, Bi 0.5K 0.5TiO 3And BaNb 2O 6For subsequent use.1:1 takes by weighing BaCO according to mol ratio 3And TiO 2Mixed-shaped resulting mixture A; 1:1:4 takes by weighing Bi according to mol ratio 2O 3, K 2CO 3And TiO 2Mixed-shaped resulting mixture B; 1:1 takes by weighing BaCO according to mol ratio 3And Nb 2O 5Mixed-shaped resulting mixture C.
Step 2: get mixture A, B, C, respectively with zirconium ballstone and deionized water, be 1:1 according to mass ratio: 1 carry out ball milling, oven dry, briquetting successively after mixing after, place 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, for subsequent use;
Step 3: with pure phase BaTiO 3Ratio is 90mol%, pure phase Bi 0.5K 0.5TiO 3Ratio is the 10mol% meter, forms mixture D after mixing, and gets mixture D and zirconium ballstone and deionized water, is 1 according to mass ratio: after carrying out ball milling, oven dry, briquetting successively after 1:1 mixes, place retort furnace to form principal crystalline phase Ba in 1100 ℃ of insulations pre-burning in 2 hours 0.9(Bi 0.5K 0.5) 0.1TiO 3Powder, for subsequent use;
Step 4: with principal crystalline phase Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3With pure phase BaNb 2O 6Powder is the 1mol meter altogether, takes by weighing 1mol%BaNb according to molar content 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 after 1:1:1 mixes, sieve according to mass ratio, forms the granulation material;
Step 6: step 5 gained granulation material is made sample under the pressure of 120MPa, then, place in the inherent high temperature box furnace of aluminum oxide saggar take zirconium white as backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 3 hours when being warming up to 1250 ℃ with 5 ℃/min, afterwards, be cooled to 500 ℃ with 5 ℃/min after, cool to room temperature with the furnace;
Step 7: behind polishing, the sample that sinters of cleaning step six, evenly apply silver electrode paste at the 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 insulation degree is stablized X8R type ceramic capacitor dielectric material, and its prescription is (1-x) Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3+ xBaNb 2O 6, x=0.02(molar percentage wherein);
Step 1: preparation BaTiO 3, Bi 0.5K 0.5TiO 3And BaNb 2O 6For subsequent use.1:1 takes by weighing BaCO according to mol ratio 3And TiO 2Mixed-shaped resulting mixture A; 1:1:4 takes by weighing Bi according to mol ratio 2O 3, K 2CO 3And TiO 2Mixed-shaped resulting mixture B; 1:1 takes by weighing BaCO according to mol ratio 3And Nb 2O 5Mixed-shaped resulting mixture C.
Step 2: get mixture A, B, C, respectively with zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixes after, place 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, for subsequent use;
Step 3: with pure phase BaTiO 3Ratio is 90mol%, pure phase Bi 0.5K 0.5TiO 3Ratio is 10%mol meter, forms mixture D after mixing, and gets mixture D and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixes after, place retort furnace in 1100 ℃ of insulations pre-burning in 2 hours formation principal crystalline phase Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3Powder, for subsequent use;
Step 4: with principal crystalline phase Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3With pure phase BaNb 2O 6Powder is the 1mol meter altogether, takes by weighing 2mol%BaNb according to molar content 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 the granulation material;
Step 6: step 5 gained granulation material is made sample under the pressure of 120MPa, then, place in the inherent high temperature box furnace of aluminum oxide saggar take zirconium white as backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 3 hours when being warming up to 1240 ℃ with 5 ℃/min, afterwards, be cooled to 500 ℃ with 5 ℃/min after, cool to room temperature with the furnace;
Step 7: behind polishing, the sample that sinters of cleaning step six, evenly apply silver electrode paste at the 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 insulation degree is stablized X8R type ceramic capacitor dielectric material, and its prescription is (1-x) Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3+ xBaNb 2O 6, x=0.03(molar percentage wherein);
Step 1: preparation BaTiO 3, Bi 0.5K 0.5TiO 3And BaNb 2O 6For subsequent use.1:1 takes by weighing BaCO according to mol ratio 3And TiO 2Mixed-shaped resulting mixture A; 1:1:4 takes by weighing Bi according to mol ratio 2O 3, K 2CO 3And TiO 2Mixed-shaped resulting mixture B; 1:1 takes by weighing BaCO according to mol ratio 3And Nb 2O 5Mixed-shaped resulting mixture C.
Step 2: get mixture A, B, C, respectively with zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixes after, place 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, for subsequent use;
Step 3: with pure phase BaTiO 3Ratio is 90mol%, pure phase Bi 0.5K 0.5TiO 3Ratio is 10%mol meter, forms mixture D after mixing, and gets mixture D and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixes after, place retort furnace in 1100 ℃ of insulations pre-burning in 2 hours formation principal crystalline phase Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3Powder, for subsequent use;
Step 4: with principal crystalline phase Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3With pure phase BaNb 2O 6Powder is the 1mol meter altogether, takes by weighing 3mol%BaNb according to molar content 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 the granulation material;
Step 6: step 5 gained granulation material is made sample under the pressure of 120MPa, then, place in the inherent high temperature box furnace of aluminum oxide saggar take zirconium white as backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 3 hours when being warming up to 1230 ℃ with 5 ℃/min, afterwards, be cooled to 500 ℃ with 5 ℃/min after, cool to room temperature with the furnace;
Step 7: behind polishing, the sample that sinters of cleaning step six, evenly apply silver electrode paste at the 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 insulation degree is stablized X8R type ceramic capacitor dielectric material, and its prescription is (1-x) Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3+ xBaNb 2O 6, x=0.04(molar percentage wherein);
Step 1: preparation BaTiO 3, Bi 0.5K 0.5TiO 3And BaNb 2O 6For subsequent use.Take by weighing BaCO at 1: 1 according to mol ratio 3And TiO 2Mixed-shaped resulting mixture A; 1:1:4 takes by weighing Bi according to mol ratio 2O 3, K 2CO 3And TiO 2Mixed-shaped resulting mixture B; 1:1 takes by weighing BaCO according to mol ratio 3And Nb 2O 5Mixed-shaped resulting mixture C.
Step 2: get mixture A, B, C, respectively with zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixes after, place 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, for subsequent use;
Step 3: with pure phase BaTiO 3Ratio is 90mol%, pure phase Bi 0.5K 0.5TiO 3Ratio is 10%mol meter, forms mixture D after mixing, and gets mixture D and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixes after, place retort furnace in 1100 ℃ of insulations pre-burning in 2 hours formation principal crystalline phase Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3Powder, for subsequent use;
Step 4: with principal crystalline phase Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3With pure phase BaNb 2O 6Powder is the 1mol meter altogether, takes by weighing 4mol%BaNb according to molar content 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 the granulation material;
Step 6: step 5 gained granulation material is made sample under the pressure of 120MPa, then, place in the inherent high temperature box furnace of aluminum oxide saggar take zirconium white as backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 3 hours when being warming up to 1220 ℃ with 5 ℃/min, afterwards, be cooled to 500 ℃ with 5 ℃/min after, cool to room temperature with the furnace;
Step 7: behind polishing, the sample that sinters of cleaning step six, evenly apply silver electrode paste at the sample tow sides, in 600 ℃ of sintering 20 minutes, obtain BaTiO 3Base lead-free X 8 R type ceramic capacitor material sample.
See also Fig. 1 to shown in Figure 8, the dielectric properties test 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 the ceramics sample of table 1 embodiment 1-4 preparation
By doping K 0.5Bi 0.5TiO 3, and and BaTiO 3Form sosoloid, can effectively improve Curie temperature, the Curie peak is moved to the 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.Simultaneously, form the fluctuating of micro components, the composition fluctuation theory is based on compound ion stochastic distribution phenomenon and proposes.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 have slightly different Curie temperature, produce the transition temperature area of broadening on the macroscopic view, even the average component of microcell is identical, also may form owing to cell configuration is different the different microcell of structure, thereby produce the disperse phase transformation.Scantlings of the structure by doping or change crystal grain, the Curie temperature of ferroelectric ceramic(s) is changed, the specific inductivity of peak value both sides rises, the warm curve that namely is situated between becomes more extensive, smooth, this by mixing or changing the effect that the crystalline-granular texture size improves 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 higher specific inductivity, low dielectric loss, body resistivity is large, temperature stability is good, being expected to substitute the lead base stupalith becomes laminated ceramic capacitor one of the excellent important candidate material of holding concurrently technically and economically.

Claims (9)

1. 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 6For subsequent use; 1:1 takes by weighing BaCO according to mol ratio 3And TiO 2Mixed-shaped resulting mixture A; 1:1:4 takes by weighing Bi according to mol ratio 2O 3, K 2CO 3And TiO 2Mixed-shaped resulting mixture B; 1:1 takes by weighing BaCO according to mol ratio 3And Nb 2O 5Mixed-shaped resulting mixture C;
Step 2: get mixture A, B, C, respectively with zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixes after, place 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, for subsequent use;
Step 3: with pure phase BaTiO 3Ratio is 90mol%, pure phase Bi 0.5K 0.5TiO 3Ratio forms mixture D for being 10mol% meter after mixing, and gets mixture D and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixes after, place retort furnace to be incubated pre-burning in 2 hours formation principal crystalline phase Ba in 1100 ℃ 0.9(Bi 0.5K 0.5) 0.1TiO 3Powder, for subsequent use;
Step 4: with principal crystalline phase Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3With pure phase BaNb 2O 6Powder is the 1mol meter altogether, takes by weighing 1～4mol%BaNb according to molar content 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 the granulation material;
Step 6: step 5 gained granulation material is made sample under the pressure of 120MPa, then, place in the inherent high temperature box furnace of aluminum oxide saggar take zirconium white as backing plate, be warming up to 500 ℃ of insulation 60min with 2 ℃/min, insulation is 3 hours when being warming up to 1220～1250 ℃ with 5 ℃/min, afterwards, be cooled to 500 ℃ with 5 ℃/min after, cool to room temperature with the furnace;
Step 7: behind polishing, the sample that sinters of cleaning step six, evenly apply silver electrode paste at the 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, it is characterized in that: in the 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 the step 5, form the oven dry material after full batching, zirconium ballstone and deionized water mixing, ball milling, the oven dry, be that 4～6% tackiness agent is added into and wherein carries out granulation with mass concentration, tackiness agent accounts for 8～10% of oven dry 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, it 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, it is characterized in that: the amount of the mixture C pre-synthesis material that takes by weighing according to molar content in the step 4 is 1mol%, 2mol%, 3mol% or 4mol%.
6. according to any one the described BaTiO in the 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, it 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 6Major ingredient and auxiliary material mixed-shaped are helped 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 prescription is (1-x) Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3+ xBaNb 2O 6, x=0.01～0.04 wherein, x is molar percentage.
8. BaTiO 3Base lead-free X 8 R type ceramic capacitor dielectric material is characterized in that: its prescription is (1-x) Ba 0.9(Bi 0.5K 0.5) 0.1TiO 3+ xBaNb 2O 6, x=0.01～0.04 wherein, x is molar percentage.
9. a kind of BaTiO as claimed in claim 8 3Base lead-free X 8 R type ceramic capacitor dielectric material is characterized in that: x=0.01,0.02,0.03 or 0.04.
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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
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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
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
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
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
CN110423111A (en) * 2019-07-30 2019-11-08 陕西科技大学 A kind of high energy-storage property lead-free ceramics material of environment-friendly type and preparation method thereof
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

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