CN107253857A - A kind of unleaded high energy storage density ceramic material and preparation method thereof - Google Patents

A kind of unleaded high energy storage density ceramic material and preparation method thereof Download PDF

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CN107253857A
CN107253857A CN201710495887.XA CN201710495887A CN107253857A CN 107253857 A CN107253857 A CN 107253857A CN 201710495887 A CN201710495887 A CN 201710495887A CN 107253857 A CN107253857 A CN 107253857A
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energy storage
high energy
ceramic material
storage density
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蒲永平
崔晨薇
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a kind of unleaded high energy storage density ceramic material and preparation method thereof, it is first according to the raw material that mol ratio weighs respective quality respectively, synthesize SNBT powders and potassium niobate powder, and mix SNBT powders after progress ball milling, drying, briquetting with potassium niobate powder, MgO powders, form full dispensing, then full dispensing is carried out to 120 mesh sievings successively, sieving materials are formed；Secondly sieving is pressed into sample, and the sample made is sintered obtains sintered specimen；Finally polish, clean sintered specimen, the sintered specimen tow sides after polishing and cleaning uniformly coat silver electrode paste, the sample for coating silver electrode is sintered and obtains SNBT bases ceramics.The unleaded high energy storage density ceramic material of SNBT bases that profit is obtained by the present invention not only has high energy storage density, and preparation technology is simple, the cost of material is low, environmental protection, is used as high-end commercial Application material excellent important candidate material simultaneous technically and economically as lead base ceramic material is substituted.

Description

A kind of unleaded high energy storage density ceramic material and preparation method thereof
Technical field
The present invention relates to ceramic capacitor material field, and in particular to a kind of unleaded high energy storage density ceramic material and its system Preparation Method.
Background technology
With the growing demand of hyundai electronicses and power equipment to electronic product, with high energy storage density Dielectric substance has been attracted wide attention.Discharge energy density highest is with dielectric constant (εr) and disruptive field intensity (Eb) increasing Plus and increase.There is different types of material, such as ferroelectric, antiferroelectric and linear dielectric in energy stores performance, it has There are different energy storage characteristics.
Due to polarization P greatly, many researchs are concentrated on ferroelectric, but their EbIt is generally relatively low.In addition, by In its high εrWith the special shape of polarized electric field (P-E) ring, so selection antiferroelectric ceramics.However, their application by To the limitation of several properties, such as caused low EbWith their high residual polarization (Pr) cause very small polarization poor.For line Property dielectric, they generally have low εr, but can be achieved on higher E compared with ferroelectric and antiferroelectricb.Therefore, only grind It is far from being enough to study carefully a type of material.In order to reach high energy storage density, it is necessary to by doping or composite modified find New base material.Therefore, look for widening the task of the temperature span of ceramic capacitor material energy normal work in itself from material Through having put on schedule by people.
In the energy storage system based on NBT of report, (1-x) Na0.5Bi0.5TiO3-xSrTiO3(NBT-ST) it is phase To the newer matrix used.However, the energy density values obtained are unsatisfactory.In work before us, it has been found that Sr0.5Na0.25Bi0.25TiO3Energy storage density of the sample when the electric field of application is 17.97kV/mm is 1.35J/cm3, with big Maximum polarization (Pm) (~34.21 μ C/cm2), but relatively large residual polarization (Pr) (~10 μ C/cm2).Therefore, it is necessary to protect The high P of cardmWith high EbOn the premise of, P is effectively reduced by doping vario-propertyr, so as to inherently improve energy-storage property.
The content of the invention
It is above-mentioned to overcome it is an object of the invention to provide a kind of unleaded high energy storage density ceramic material and preparation method thereof The defect that prior art is present, the ceramic material that profit is obtained by the present invention not only has good temperature in wide warm area Stable type, and higher dielectric constant and relatively low dielectric loss, preparation technology are simple, and the cost of material is low, environment-friendly.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of unleaded high energy storage density ceramic material, the stoichiometric equation of described unleaded high energy storage density ceramic material is (1-x)Sr0.5Na0.25Bi0.25TiO3- 5wt%MgO-xKNbO3, wherein x=1~9mol%.
A kind of preparation method of unleaded high energy storage density ceramic material, comprises the following steps：
Step one：Weigh the Na of respective quality respectively according to mol ratio2CO3、Bi2O3、SrCO3、TiO2、K2CO3、Nb2O5, Synthesize Sr0.5Na0.25Bi0.25TiO3Powder and KNbO3Powder, then according to stoichiometric equation (1-x) (Bi0.5Na0.5TiO3)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3, x=1~9mol% takes Sr0.5Na0.25Bi0.25TiO3Powder, MgO powders and KNbO3 Powder is well mixed to form full dispensing；
Step 2：Ball milling, drying, sieving are carried out after full dispensing is mixed with zirconium oxide ballstone, deionized water, sieving is formed Material；
Step 3：By sieving materials under 190~210MPa pressure, sample is pressed into by isostatic cool pressing, and will make Sample carry out high temperature sintering obtain sintered specimen；
Step 4：The sintered specimen that polishing, cleaning step three are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample for coating silver electrode is sintered and obtains Sr0.5Na0.25Bi0.25TiO3The unleaded high storage of base Can density ceramic.
Further, Sr in step one0.5Na0.25Bi0.25TiO3The preparation process of powder includes：It is first according to mol ratio 4: 1:1:8 weigh SrCO3、Bi2O3、Na2CO3And TiO2It is mixed to form mixture A；Then mixture A, zirconium ballstone and deionized water are taken It is 1 according to mass ratio:2:(0.8~1) ball milling, drying and briquetting are carried out successively after mixing, most after 1000~1150 DEG C of insulations 2.5~3 hours, obtain the Sr of pure phase0.5Na0.25Bi0.25TiO3Powder.
Further, KNbO in step one3The preparation process of powder includes：It is first according to mol ratio 1:1 weighs Nb2O5With K2CO3It is mixed to form mixture B；Then it is 1 according to mass ratio to take mixture B, zirconium ballstone and deionized water:2:(1~1.2) mix Ball milling, drying and briquetting are carried out after conjunction successively, most 2~3 hours is incubated after 790~820 DEG C, obtains the KNbO of pure phase3Powder.
Further, in step 2 by full dispensing and zirconium oxide ballstone, deionized water according to mass ratio 1:(1.8~2.1): (0.7~1.1) ball milling is carried out after mixing.
Further, the Ball-milling Time in step 2 is 20~24h.
Further, sieve mesh number is 120 mesh when being sieved in step 2.
Further, the sintering process in step 3 is specially：Be warming up to 200 DEG C first with 2 DEG C/min, then with 3 DEG C/ Min is warming up to 500 DEG C, then is warming up to 1000 DEG C with 5 DEG C/min, and 3 are incubated when being then warming up to 1230~1260 DEG C with 3 DEG C/min ~4 hours；Afterwards, 1000 DEG C are cooled to 3 DEG C/min, then 500 DEG C is cooled to 5 DEG C/min, finally cool to room temperature with the furnace.
Further, the sintering condition in step 4 is：25~30min is sintered at a temperature of 550~600 DEG C.
Compared with prior art, the present invention has following beneficial technique effect：
Sr prepared by the inventive method0.5Na0.25Bi0.25TiO3The unleaded high energy storage density ceramic material of base, not only with height Energy storage density, and preparation technology is simple, and the cost of material is low, environmental protection, as substitute lead base ceramic material be used as it is high-end Commercial Application material excellent important candidate material simultaneous technically and economically.The present invention is with Sr0.5Na0.25Bi0.25TiO3It is used as base Body, passes through (Na0.5Bi0.5)2+Ion doping enters A, introduces and Sr2+Ionic radiusDifferent (Na0.5Bi0.5)2+ IonGeneration distortion of lattice, inherently realizes the raising of ceramic polarization intensity.It is logical Cross introducing KNbO3(KN) this kind of niobates introduces Sr0.5Na0.25Bi0.25TiO3Solid solution is formed, to be effectively reduced Pr, pass through KN The change and MgO a small amount of introducing of doping concentration, to realize the ceramic relatively low P of the systemrHigher EbCarry out controllable tune simultaneously Section, to obtain high energy storage density.
Brief description of the drawings
Fig. 1 is (1-x) Sr0.5Na0.25Bi0.25TiO3- 5wt%MgO-xKNbO3The XRD of system ceramics；
Fig. 2 is that energy storage density calculates schematic diagram；
Fig. 3 is (1-x) Sr0.5Na0.25Bi0.25TiO3- 5wt%MgO-xKNbO3System ceramics polarization intensity-electric-field intensity Curve；
Fig. 4 is (1-x) Sr0.5Na0.25Bi0.25TiO3- 5wt%MgO-xKNbO3System ceramics PrWith x variation diagrams；
Fig. 5 is (1-x) Sr0.5Na0.25Bi0.25TiO3- 5wt%MgO-xKNbO3System ceramics Jd, JcAnd η change with x Figure.
Embodiment
Embodiments of the present invention are described in further detail below：
A kind of Sr0.5Na0.25Bi0.25TiO3The unleaded high energy storage density ceramic material of base, its stoichiometric equation is (1-x) Sr0.5Na0.25Bi0.25TiO3- 5wt%MgO-xKNbO3, wherein x=1~9mol%.
A kind of Sr0.5Na0.25Bi0.25TiO3Unleaded high energy storage density ceramic material of base and preparation method thereof, including following step Suddenly：
Step one：Prepare pure phase Sr0.5Na0.25Bi0.25TiO3With pure phase KNbO3It is standby.According to mol ratio 4:1:1:8 weigh SrCO3、Bi2O3、Na2CO3And TiO2It is mixed to form mixture A；According to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixed Compound B.MgO、SrCO3, Bi2O3, Na2CO3、TiO2、Nb2O5And K2CO3Purity be more than 98.0%.
Step 2：Take mixture A, B, respectively with zirconium ballstone and deionized water, according to mass ratio be 1:2:(0.8~1), 1: 2:(1~1.2) after mixing, using planetary ball mill 20~24h of ball milling, then after 85 DEG C dry 14~16h, briquetting, it is placed in 2.5~3 hours are incubated respectively at 1000~1150 DEG C in batch-type furnace, 790~820 DEG C of insulations are formed for 2~3 hours respectively Sr0.5Na0.25Bi0.25TiO3Powder and KNbO3Powder, it is standby；
Step 3：According to chemical formula (1-x) (Bi0.5Na0.5TiO3)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3, x=1~ 9mol%, takes Sr0.5Na0.25Bi0.25TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing, and will match somebody with somebody entirely Material is with zirconium oxide ballstone, deionized water according to mass ratio 1:(1.8~2.1):(0.7~1.1) mix after carry out ball milling 20~ 24h, drying, obtain drying material；
Step 4：By ground 120 mesh sieve of drying material, sieving materials are formed；
Step 5：The sieving materials that step 4 is obtained are pressed into examination under 190~210MPa pressure by isostatic cool pressing Sample, and the sample made is placed in the aluminum oxide saggar using zirconium oxide as backing plate, aluminum oxide saggar then is placed in into microwave burns It is sintered in freezing of a furnace and obtains sintered specimen, wherein sintering condition is：200 DEG C are warming up to 2 DEG C/min first, with 3 DEG C/min 500 DEG C are warming up to, 1000 DEG C are warming up to 5 DEG C/min, insulation 3~4 is small when being then warming up to 1230~1260 DEG C with 3 DEG C/min When；Afterwards, 1000 DEG C are cooled to 3 DEG C/min, then 500 DEG C is cooled to 5 DEG C/min, finally cool to room temperature with the furnace；
Step 6：The sintered specimen that polishing, cleaning step five are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample for coating silver electrode is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then will Aluminum oxide saggar is placed in batch-type furnace, and 25~30min is sintered at a temperature of 550~600 DEG C and obtains (1-x) SNBTM5-xKN bodies System's ceramics.
The present invention is described in further detail with reference to embodiment：
Blank Example
Sr of the present invention0.5Na0.25Bi0.25TiO3The unleaded high energy storage density ceramic material of base, it is (1-x) SNBTM5- that it, which is formulated, XKN, wherein x=0.
Step one：Prepare pure phase Sr0.5Na0.25Bi0.25TiO3With pure phase KNbO3It is standby.According to mol ratio 4:1:1:8 weigh SrCO3、Bi2O3、Na2CO3And TiO2It is mixed to form mixture A；According to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixed Compound B.MgO、SrCO3, Bi2O3, Na2CO3、TiO2、Nb2O5And K2CO3Purity be more than 98.0%.
Step 2：Take mixture A, B, respectively with zirconium ballstone and deionized water, according to mass ratio be 1:2:0.8、1:2:1 mixes After conjunction, using planetary ball mill ball milling 20h, then after 85 DEG C dry 14h, briquetting, it is placed in batch-type furnace respectively at 1000 DEG C Insulation 3 hours, 790 DEG C of insulations form Sr in 3 hours respectively0.5Na0.25Bi0.25TiO3Powder and KNbO3Powder, it is standby；
Step 3：According to chemical formula (Bi0.5Na0.5TiO3)0.5Sr0.5TiO3- 5wt%MgO, takes Sr0.5Na0.25Bi0.25TiO3 Powder, MgO powders are well mixed to form full dispensing, and by full dispensing and zirconium oxide ballstone, deionized water, according to mass ratio 1: 1.8:Ball milling 20h, drying are carried out after 0.7 mixing, drying material is obtained；
Step 4：By ground 120 mesh sieve of drying material, sieving materials are formed；
Step 5：The sieving materials that step 4 is obtained are pressed into sample under 190MPa pressure by isostatic cool pressing, and The sample made is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then aluminum oxide saggar is placed in microwave agglomerating furnace It is sintered and obtains sintered specimen, wherein sintering condition is：200 DEG C are warming up to 2 DEG C/min first, is warming up to 3 DEG C/min 500 DEG C, 1000 DEG C are warming up to 5 DEG C/min, 3 hours are incubated when being then warming up to 1260 DEG C with 3 DEG C/min；Afterwards, with 3 DEG C/ Min is cooled to 1000 DEG C, then is cooled to 500 DEG C with 5 DEG C/min, finally cools to room temperature with the furnace；
Step 6：The sintered specimen that polishing, cleaning step five are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample for coating silver electrode is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then will Aluminum oxide saggar is placed in batch-type furnace, and 25min is sintered at a temperature of 550 DEG C and obtains SNBTM5 systems ceramics.
Embodiment 1
Sr of the present invention0.5Na0.25Bi0.25TiO3The unleaded high energy storage density ceramic material of base, it is (1-x) SNBTM5- that it, which is formulated, XKN, wherein x=0.01.
Step one：Prepare pure phase Sr0.5Na0.25Bi0.25TiO3With pure phase KNbO3It is standby.According to mol ratio 4:1:1:8 weigh SrCO3、Bi2O3、Na2CO3And TiO2It is mixed to form mixture A；According to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixed Compound B.MgO、SrCO3, Bi2O3, Na2CO3、TiO2、Nb2O5And K2CO3Purity be more than 98.0%.
Step 2：Take mixture A, B, respectively with zirconium ballstone and deionized water, according to mass ratio be 1:2:1、1:2:1.2 it is mixed After conjunction, using planetary ball mill ball milling 24h, then after 85 DEG C dry 16h, briquetting, it is placed in batch-type furnace respectively at 1150 DEG C Insulation 2.5 hours, 820 DEG C of insulations form Sr in 2 hours respectively0.5Na0.25Bi0.25TiO3Powder and KNbO3Powder, it is standby；
Step 3：According to (the Bi of chemical formula 0.990.5Na0.5TiO3)0.5Sr0.5TiO3- 5wt%MgO-0.01KNbO3, take Sr0.5Na0.25Bi0.25TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing, and by full dispensing and zirconium oxide Ballstone, deionized water, according to mass ratio 1:2.1:Ball milling 24h, drying are carried out after 1.1 mixing, drying material is obtained；
Step 4：By ground 120 mesh sieve of drying material, sieving materials are formed；
Step 5：The sieving materials that step 4 is obtained are pressed into sample under 190MPa pressure by isostatic cool pressing, and The sample made is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then aluminum oxide saggar is placed in microwave agglomerating furnace It is sintered and obtains sintered specimen, wherein sintering condition is：200 DEG C are warming up to 2 DEG C/min first, is warming up to 3 DEG C/min 500 DEG C, 1000 DEG C are warming up to 5 DEG C/min, 3 hours are incubated when being then warming up to 1260 DEG C with 3 DEG C/min；Afterwards, with 3 DEG C/ Min is cooled to 1000 DEG C, then is cooled to 500 DEG C with 5 DEG C/min, finally cools to room temperature with the furnace；
Step 6：The sintered specimen that polishing, cleaning step five are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample for coating silver electrode is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then will Aluminum oxide saggar is placed in batch-type furnace, and 25min is sintered at a temperature of 550 DEG C and obtains 0.99SNBTM5-0.01KN systems ceramics.
Embodiment 2
Sr of the present invention0.5Na0.25Bi0.25TiO3The unleaded high energy storage density ceramic material of base, it is (1-x) SNBTM5- that it, which is formulated, XKN, wherein x=0.03.
Step one：Prepare pure phase Sr0.5Na0.25Bi0.25TiO3With pure phase KNbO3It is standby.According to mol ratio 4:1:1:8 weigh SrCO3、Bi2O3、Na2CO3And TiO2It is mixed to form mixture A；According to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixed Compound B.MgO、SrCO3, Bi2O3, Na2CO3、TiO2、Nb2O5And K2CO3Purity be more than 98.0%.
Step 2：Take mixture A, B, respectively with zirconium ballstone and deionized water, according to mass ratio be 1:2:0.9、1:2:1.1 After mixing, using planetary ball mill ball milling 22h, then after 85 DEG C dry 15h, briquetting, it is placed in batch-type furnace respectively at 1100 DEG C insulation 2.8 hours, 810 DEG C of insulations form Sr in 2.5 hours respectively0.5Na0.25Bi0.25TiO3Powder and KNbO3Powder, it is standby；
Step 3：According to (the Bi of chemical formula 0.970.5Na0.5TiO3)0.5Sr0.5TiO3- 5wt%MgO-0.03KNbO3, take Sr0.5Na0.25Bi0.25TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing, and by full dispensing and zirconium oxide Ballstone, deionized water, according to mass ratio 1:1.9:Ball milling 22h, drying are carried out after 0.8 mixing, drying material is obtained；
Step 4：By ground 120 mesh sieve of drying material, sieving materials are formed；
Step 5：The sieving materials that step 4 is obtained are pressed into sample under 200MPa pressure by isostatic cool pressing, and The sample made is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then aluminum oxide saggar is placed in microwave agglomerating furnace It is sintered and obtains sintered specimen, wherein sintering condition is：200 DEG C are warming up to 2 DEG C/min first, is warming up to 3 DEG C/min 500 DEG C, 1000 DEG C are warming up to 5 DEG C/min, 3 hours are incubated when being then warming up to 1250 DEG C with 3 DEG C/min；Afterwards, with 3 DEG C/ Min is cooled to 1000 DEG C, then is cooled to 500 DEG C with 5 DEG C/min, finally cools to room temperature with the furnace；
Step 6：The sintered specimen that polishing, cleaning step five are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample for coating silver electrode is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then will Aluminum oxide saggar is placed in batch-type furnace, and 25min is sintered at a temperature of 550 DEG C and obtains 0.97SNBTM5-0.03KN systems ceramics.
Embodiment 3
Sr of the present invention0.5Na0.25Bi0.25TiO3The unleaded high energy storage density ceramic material of base, it is (1-x) SNBTM5- that it, which is formulated, XKN, wherein x=0.05.
Step one：Prepare pure phase Sr0.5Na0.25Bi0.25TiO3With pure phase KNbO3It is standby.According to mol ratio 4:1:1:8 weigh SrCO3、Bi2O3、Na2CO3And TiO2It is mixed to form mixture A；According to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixed Compound B.MgO、SrCO3, Bi2O3, Na2CO3、TiO2、Nb2O5And K2CO3Purity be more than 98.0%.
Step 2：Take mixture A, B, respectively with zirconium ballstone and deionized water, according to mass ratio be 1:2:1、1:2:1.2 it is mixed After conjunction, using planetary ball mill ball milling 23h, then after 85 DEG C dry 15h, briquetting, it is placed in batch-type furnace respectively at 1125 DEG C Insulation 3 hours, 815 DEG C of insulations form Sr in 2 hours respectively0.5Na0.25Bi0.25TiO3Powder and KNbO3Powder, it is standby；
Step 3：According to (the Bi of chemical formula 0.950.5Na0.5TiO3)0.5Sr0.5TiO3- 5wt%MgO-0.05KNbO3, take Sr0.5Na0.25Bi0.25TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing, and by full dispensing and zirconium oxide Ballstone, deionized water, according to mass ratio 1:2:Ball milling 23h, drying are carried out after 0.9 mixing, drying material is obtained；
Step 4：By ground 120 mesh sieve of drying material, sieving materials are formed；
Step 5：The sieving materials that step 4 is obtained are pressed into sample under 200MPa pressure by isostatic cool pressing, and The sample made is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then aluminum oxide saggar is placed in microwave agglomerating furnace It is sintered and obtains sintered specimen, wherein sintering condition is：200 DEG C are warming up to 2 DEG C/min first, is warming up to 3 DEG C/min 500 DEG C, 1000 DEG C are warming up to 5 DEG C/min, 4 hours are incubated when being then warming up to 1240 DEG C with 3 DEG C/min；Afterwards, with 3 DEG C/ Min is cooled to 1000 DEG C, then is cooled to 500 DEG C with 5 DEG C/min, finally cools to room temperature with the furnace；
Step 6：The sintered specimen that polishing, cleaning step five are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample for coating silver electrode is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then will Aluminum oxide saggar is placed in batch-type furnace, and 30min is sintered at a temperature of 600 DEG C and obtains 0.95SNBTM5-0.05KN systems ceramics.
Embodiment 4
Sr of the present invention0.5Na0.25Bi0.25TiO3The unleaded high energy storage density ceramic material of base, it is (1-x) SNBTM5- that it, which is formulated, XKN, wherein x=0.07.
Step one：Prepare pure phase Sr0.5Na0.25Bi0.25TiO3With pure phase KNbO3It is standby.According to mol ratio 4:1:1:8 weigh SrCO3、Bi2O3、Na2CO3And TiO2It is mixed to form mixture A；According to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixed Compound B.MgO、SrCO3, Bi2O3, Na2CO3、TiO2、Nb2O5And K2CO3Purity be more than 98.0%.
Step 2：Take mixture A, B, respectively with zirconium ballstone and deionized water, according to mass ratio be 1:2:0.9、1:2:1 mixes After conjunction, using planetary ball mill ball milling 21h, then after 85 DEG C dry 16h, briquetting, it is placed in batch-type furnace respectively at 1080 DEG C Insulation 3 hours, 820 DEG C of insulations form Sr in 2 hours respectively0.5Na0.25Bi0.25TiO3Powder and KNbO3Powder, it is standby；
Step 3：According to (the Bi of chemical formula 0.930.5Na0.5TiO3)0.5Sr0.5TiO3- 5wt%MgO-0.07KNbO3, take Sr0.5Na0.25Bi0.25TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing, and by full dispensing and zirconium oxide Ballstone, deionized water, according to mass ratio 1:2:Ball milling 21h, drying are carried out after 0.8 mixing, drying material is obtained；
Step 4：By ground 120 mesh sieve of drying material, sieving materials are formed；
Step 5：The sieving materials that step 4 is obtained are pressed into sample under 210MPa pressure by isostatic cool pressing, and The sample made is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then aluminum oxide saggar is placed in microwave agglomerating furnace It is sintered and obtains sintered specimen, wherein sintering condition is：200 DEG C are warming up to 2 DEG C/min first, is warming up to 3 DEG C/min 500 DEG C, 1000 DEG C are warming up to 5 DEG C/min, 4 hours are incubated when being then warming up to 1230 DEG C with 3 DEG C/min；Afterwards, with 3 DEG C/ Min is cooled to 1000 DEG C, then is cooled to 500 DEG C with 5 DEG C/min, finally cools to room temperature with the furnace；
Step 6：The sintered specimen that polishing, cleaning step five are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample for coating silver electrode is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then will Aluminum oxide saggar is placed in batch-type furnace, and 30min is sintered at a temperature of 600 DEG C and obtains 0.93SNBTM5-0.07KN systems ceramics.
Embodiment 5
Sr of the present invention0.5Na0.25Bi0.25TiO3The unleaded high energy storage density ceramic material of base, it is (1-x) SNBTM5- that it, which is formulated, XKN, wherein x=0.09.
Step one：Prepare pure phase Sr0.5Na0.25Bi0.25TiO3With pure phase KNbO3It is standby.According to mol ratio 4:1:1:8 weigh SrCO3、Bi2O3、Na2CO3And TiO2It is mixed to form mixture A；According to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixed Compound B.MgO、SrCO3, Bi2O3, Na2CO3、TiO2、Nb2O5And K2CO3Purity be more than 98.0%.
Step 2：Take mixture A, B, respectively with zirconium ballstone and deionized water, according to mass ratio be 1:2:1、1:2:1.2 it is mixed After conjunction, using planetary ball mill ball milling 20h, then after 85 DEG C dry 16h, briquetting, it is placed in batch-type furnace respectively at 1150 DEG C Insulation 3 hours, 790 DEG C of insulations form Sr in 3 hours respectively0.5Na0.25Bi0.25TiO3Powder and KNbO3Powder, it is standby；
Step 3：According to (the Bi of chemical formula 0.910.5Na0.5TiO3)0.5Sr0.5TiO3- 5wt%MgO-0.09KNbO3, take Sr0.5Na0.25Bi0.25TiO3Powder, MgO powders and KNbO3Powder is well mixed to form full dispensing, and by full dispensing and zirconium oxide Ballstone, deionized water, according to mass ratio 1:2.1:Ball milling 21h, drying are carried out after 0.7 mixing, drying material is obtained；
Step 4：By ground 120 mesh sieve of drying material, sieving materials are formed；
Step 5：The sieving materials that step 4 is obtained are pressed into sample under 210MPa pressure by isostatic cool pressing, and The sample made is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then aluminum oxide saggar is placed in microwave agglomerating furnace It is sintered and obtains sintered specimen, wherein sintering condition is：200 DEG C are warming up to 2 DEG C/min first, is warming up to 3 DEG C/min 500 DEG C, 1000 DEG C are warming up to 5 DEG C/min, 4 hours are incubated when being then warming up to 1230 DEG C with 3 DEG C/min；Afterwards, with 3 DEG C/ Min is cooled to 1000 DEG C, then is cooled to 500 DEG C with 5 DEG C/min, finally cools to room temperature with the furnace；
Step 6：The sintered specimen that polishing, cleaning step five are obtained, the sintered specimen tow sides after polishing and cleaning Uniform coating silver electrode paste, the sample for coating silver electrode is placed in the aluminum oxide saggar using zirconium oxide as backing plate, then will Aluminum oxide saggar is placed in batch-type furnace, and 30min is sintered at a temperature of 600 DEG C and obtains 0.91SNBTM5-0.09KN systems ceramics.
It will be seen from figure 1 that blank example and example 1 to example 5 prepared by ceramic medium material, due to obvious (200) pseudo- Emission in Cubic is presented in peak, all samples.This shows that KN has been completely diffusing in SNBT lattices form stable consolidate Solution, and observe Mg2TiO4The generation of second phase.Mg in the present invention2TiO4Time mutually can be attributed between MgO and matrix Reaction.It is close by integrating the acquisition discharge energy-storage of the area between polarization intensity axle and the discharge curve of monopole P-E ferroelectric hysteresis loops Spend Jd.Areal calculation energy loss density J between charging and discharging curve by integrating monopole P-E ferroelectric hysteresis loopsloss.Fig. 2 is represented The schematic diagram of energy stores parameter in P-E curves, black shaded area represents recoverable energy storage density.JdIt can pass through Below equation is calculated：
Charging energy-storing density Jc：
Jc=Jd+Jloss (2)
Wherein P and E are polarization and electric field, EbIt is dielectric breakdown electric field.Energy storage efficiency (η) is equal to Jd/Jc。
Fig. 3 describes the monopole P-E ferroelectric hysteresis loops of all research compositions measured under 10Hz frequencies, is measured to it and faces Boundary's electric field.Obviously, the feature of P-E circulations is significant depends on KN contents.With the increase of KN contents, P-E curves become elongated, and And be driven plain.As shown in figure 4, residual polarization (Pr) reduce with x increase.This is relevant with the reduction of polarity phase.SNBTM5 Ceramics show 4.01 relatively large μ C/cm2Residual polarization, when KN contents increase to 9.0mol%, the value is down to 1.19μC/cm2.Small PrStored energy application is more applicable for, because electric charge can effectively discharge.Fig. 5 represents the discharge energy of ceramics Density, rechargeable energy density and energy storage efficiency.As x=0.05,17.85kV/mm maximum polarization off field, ceramic electric discharge Energy density is up to 2J/cm3.High dielectric breakdown strength is 17.85kV/mm, high maximum polarization (Pm) it is 28.91 μ C/ cm2, cause the high discharge energy density in x=0.05 samples.η and the energy density not discharged are closely related, are inversely proportional. With the increase of KN contents, η gradually increases, and the maximum of x=0.09 sample is 78.50%.Therefore, x=in the present invention 0.05 sample is the promising candidate material of high energy storage density capacitor.

Claims (9)

1. a kind of unleaded high energy storage density ceramic material, it is characterised in that the change of described unleaded high energy storage density ceramic material Metering-type is (1-x) Sr0.5Na0.25Bi0.25TiO3- 5wt%MgO-xKNbO3, wherein x=1~9mol%.
2. a kind of preparation method of unleaded high energy storage density ceramic material, it is characterised in that comprise the following steps：
Step one：Weigh the Na of respective quality respectively according to mol ratio2CO3、Bi2O3、SrCO3、TiO2、K2CO3、Nb2O5, synthesis Sr0.5Na0.25Bi0.25TiO3Powder and KNbO3Powder, then according to stoichiometric equation (1-x) (Bi0.5Na0.5TiO3)0.5Sr0.5TiO3- 5wt%MgO-xKNbO3, x=1~9mol% takes Sr0.5Na0.25Bi0.25TiO3Powder, MgO powders and KNbO3 Powder is well mixed to form full dispensing；
Step 2：Ball milling, drying, sieving are carried out after full dispensing is mixed with zirconium oxide ballstone, deionized water, sieving materials are formed；
Step 3：By sieving materials under 190~210MPa pressure, sample is pressed into by isostatic cool pressing, and by the examination made Sample carries out high temperature sintering and obtains sintered specimen；
Step 4：The sintered specimen that polishing, cleaning step three are obtained, the sintered specimen tow sides after polishing and cleaning are uniform Silver electrode paste is coated, the sample for coating silver electrode is sintered and obtains Sr0.5Na0.25Bi0.25TiO3The unleaded high energy storage of base is close Spend ceramic material.
3. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 2, it is characterised in that step Sr in one0.5Na0.25Bi0.25TiO3The preparation process of powder includes：It is first according to mol ratio 4:1:1:8 weigh SrCO3、Bi2O3、 Na2CO3And TiO2It is mixed to form mixture A；Then it is 1 according to mass ratio to take mixture A, zirconium ballstone and deionized water:2:(0.8 ~1) mix after carry out ball milling, drying and briquetting successively, most after 1000~1150 DEG C be incubated 2.5~3 hours, obtain pure phase Sr0.5Na0.25Bi0.25TiO3Powder.
4. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 2, it is characterised in that step KNbO in one3The preparation process of powder includes：It is first according to mol ratio 1:1 weighs Nb2O5And K2CO3It is mixed to form mixture B；So After take mixture B, zirconium ballstone and deionized water according to mass ratio be 1:2:(1~1.2) mix after carry out successively ball milling, drying and Briquetting, is most incubated 2~3 hours after 790~820 DEG C, obtains the KNbO of pure phase3Powder.
5. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 2, it is characterised in that step By full dispensing and zirconium oxide ballstone, deionized water according to mass ratio 1 in two:(1.8~2.1):(0.7~1.1) carried out after mixing Ball milling.
6. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 2, it is characterised in that step Ball-milling Time in two is 20~24h.
7. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 2, it is characterised in that step Sieve mesh number is 120 mesh when being sieved in two.
8. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 2, it is characterised in that step Sintering process in three is specially：200 DEG C are warming up to 2 DEG C/min first, then 500 DEG C are warming up to 3 DEG C/min, then with 5 DEG C/min is warming up to 1000 DEG C, and 3~4 hours are incubated when being then warming up to 1230~1260 DEG C with 3 DEG C/min；Afterwards, with 3 DEG C/ Min is cooled to 1000 DEG C, then is cooled to 500 DEG C with 5 DEG C/min, finally cools to room temperature with the furnace.
9. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 2, it is characterised in that step Sintering condition in four is：25~30min is sintered at a temperature of 550~600 DEG C.
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CN110759729A (en) * 2019-11-22 2020-02-07 陕西科技大学 Ceramic material with high energy storage performance and ultra-fast discharge rate and preparation method thereof
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Application publication date: 20171017