CN106542821A - A kind of Bi2O3‑B2O3ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic and preparation method thereof - Google Patents

A kind of Bi2O3‑B2O3ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic and preparation method thereof Download PDF

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CN106542821A
CN106542821A CN201610905905.2A CN201610905905A CN106542821A CN 106542821 A CN106542821 A CN 106542821A CN 201610905905 A CN201610905905 A CN 201610905905A CN 106542821 A CN106542821 A CN 106542821A
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蒲永平
王亚茹
师裕
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Shaanxi University of Science and Technology
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass

Abstract

The invention discloses a kind of Bi2O3‑B2O3ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic and preparation method thereof, including main component SrCO3、TiO2And BaCO3, auxiliary element Bi2O3‑B2O3ZnO glass.Its preparation method is：By SrCO3、TiO2And BaCO3Weigh according to certain stoichiometric proportion for raw material, ball milling, discharge post-drying, and at 1150 DEG C, pre-burning 2h, obtains Ba0.4Sr0.6TiO3Powder body.According to (100 x) wt%Ba0.4Sr0.6TiO3+ xwt%Bi2O3‑B2O3ZnO quality proportionings mixs with zirconium ballstone and deionized water after weighing, carry out successively ball milling, drying, pelletize, sieve after be pressed into sample, sinter within 2 hours in 1250～1350 DEG C of insulations in atmosphere and make, furnace cooling, last electrode coated slurry.Unleaded dielectric substance prepared by the inventive method meets topmost three features in terms of energy storage ceramic dielectric properties：High dielectric constant, low dielectric loss, high disruptive field intensity and big energy storage density, preparation process is simple are inexpensive, environmental protection.

Description

A kind of Bi2O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic and its system Preparation Method
Technical field
The present invention relates to ceramic dielectric material field, and in particular to a kind of Bi2O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic and preparation method thereof.
Background technology
In recent years, with the rise of new technology revolution, economic fast development, its demand to the energy are also continuously increased.Newly The exploitation of the energy, become the effective way for solving current energy crisis.Research and development new forms of energy so as to replace traditional energy Source, reduces the pollution to environment, it is to avoid the exhaustion of traditional energy, is the final energy demand prediction for meeting human social development.New In the exploitation of the energy, need for unidirectional current to be changed into the use of alternating current supply load, this is completed using contravariant equipment generally One transformation, and condenser ceramics is the of paramount importance element of energy conversion in contravariant equipment.Under electric field action, condenser ceramics (media ceramic) can produce polarization, can store and discharge electric charge, what capacitor was exactly fabricated by using this characteristic.
Ba1-xSrxTiO3Ceramics combine BaTiO3Ceramics and SrTiO3The premium properties of ceramics, becomes energy-storing dielectric ceramic The study hotspot in field.However, Ba1-xSrxTiO3The crystal grain and crystal boundary of abnormal growth, space, impurity etc. are there is in ceramics no Uniform microstructure, while Ba1-xSrxTiO3The dielectric loss and electrostriction effect of ceramics, can cause material to be made in electric field Occurs micro-crack with, the factor such as uneven microstructure and micro-crack makes Ba1-xSrxTiO3Ceramics will under compared with existing fringing field It is breakdown.How to improve the micro-property of ceramics, reduce dielectric loss, improve disruptive field intensity, so as to the energy storage for improving ceramics is close Degree, becomes the focus of Recent study.
The content of the invention
It is an object of the invention to provide a kind of Bi2O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic and Its preparation method, with the defect for overcoming above-mentioned prior art to exist, by accumulation energy type ceramic dielectric obtained in the inventive method Material, not only preparation process is simple, the cost of material is low, and with higher dielectric constant, low dielectric loss, high puncture Voltage and high energy storage density, it is possible to become replacement Ba0.4Sr0.6TiO3The unleaded accumulation energy type ceramic material of base is in technology and economy Upper and excellent important candidate material.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of Bi2O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic, formula are (100-x) Ba0.4Sr0.6TiO3+x Bi2O3-B2O3- ZnO, wherein x=1～9wt%, x are mass percent.
Further, x=1wt%, 3wt%, 5wt%, 7wt% or 9wt%.
A kind of Bi2O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3The preparation method of base energy storage ceramic, including following step Suddenly：
Step one：According to mol ratio 0.6:1:0.4 weighs SrCO3、TiO2And BaCO3It is mixed to form mixture A；Will mixing Thing A carries out ball milling, drying, after briquetting, is incubated 1.5～2 hours in 1120～1150 DEG C, forms the Ba of pure phase0.4Sr0.6TiO3Powder Body, it is standby；
Step 2：According to Bi2O3：B2O3：ZnO=6:3:1 mol ratio weighs raw material, adds after being fully ground stirring and evenly mixing Heat, is incubated 1.5～2h and obtains high-temperature fusant after being warming up to 1200～1300 DEG C, then by high-temperature fusant first one-step forming, treat preliminary Made annealing treatment after molding, cut after annealing, the sample of well cutting is carried out into Crystallizing treatment, Bi after cooling, is obtained2O3- B2O3- ZnO glass dust；
Step 3：By the Ba for obtaining0.4Sr0.6TiO3Powder body and Bi2O3-B2O3- ZnO glass dust is according to (100-x) Ba0.4Sr0.6TiO3+xBi2O3-B2O3- ZnO is mixed to get mixture B, take after mixture B is mixed with zirconium ballstone and deionized water according to It is secondary to carry out ball milling, drying, pelletize, sieve, granulation material is formed, wherein x=1～9wt%, x are mass percent；
Step 4：Granulation material obtained by step 3 is made into sample under the pressure of 110～120MPa, then with 2 DEG C/min 500 DEG C of insulation 60min are warming up to, and are incubated 2～3 hours, afterwards, with 5 DEG C/min when 1250～1350 DEG C are warming up to 5 DEG C/min After being cooled to 500 DEG C, room temperature is cooled to the furnace；
Step 5：After the sample that polishing, cleaning step four are sintered, silver electrode slurry is uniformly coated in sample tow sides Material, sinters 20～30 minutes in 600 DEG C, obtains Bi2O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic.
Further, in step 2, annealing is specially：Anneal in 500 DEG C of annealing furnace is warming up in advance 2h；Move back The size of 10.0mm × 10.0mm × 2.0mm is cut to after fire.
Further, in step 2, Crystallizing treatment is specially：The sample of well cutting is placed on stove heat in Muffle furnace, 4h is incubated after 700 DEG C～750 are risen to the heating rate of 10 DEG C/min.
Further, step one, Ball-milling Time is 4～6 hours in three.
Further, take in step 3 carried out after mixture B is mixed with zirconium ballstone and deionized water successively ball milling, drying after Drying material is obtained, binding agent is added into drying material carries out pelletize, binding agent accounts for 8～10%, Ran Houfen of drying material quality Do not cross 40 mesh and 80 mesh sieves take middle material and obtain granulation material.
Further, described adhesive is polyvinyl alcohol water solution.
Further, the mass concentration of binding agent is 4～6%.
Compared with prior art, the present invention has following beneficial technique effect：
The present invention is prepared using conventional solid-state method, technical maturity, is adapted to industrialization production, is employed Bi in addition2O3-B2O3- ZnO glass, is acted on using the liquid-phase sintering of glass phase, improves Ba0.4Sr0.6TiO3The microstructure of ceramics and dielectric properties, this Unleaded accumulation energy type ceramic dielectric material not only preparation process is simple prepared by inventive method, the cost of material is low, and with compared with High dielectric constant, low dielectric loss, high breakdown voltage and high energy storage density, it is intended to improve Ba0.4Sr0.6TiO3Ceramics Microstructure and improve its energy storage density.
Description of the drawings
Fig. 1 is comparative example and embodiment 1-5Ba0.4Sr0.6TiO3Ceramics sample and Bi2O3-B2O3The XRD figure of-ZnO glass, Wherein (a) is Ba0.4Sr0.6TiO3The XRD figure of ceramics sample；B () is Bi2O3-B2O3The XRD figure of-ZnO glass；
Fig. 2 is comparative example and embodiment 1-5 addition Bi2O3-B2O3The Ba of-ZnO glass0.4Sr0.6TiO3The SEM of ceramics sample Figure：(a) x=0；(b) x=1；(c) x=3；(d) x=5；(e) x=7；(f) x=9；
Fig. 3 is comparative example and embodiment 1-5 addition Bi2O3-B2O3The Ba of-ZnO glass0.4Sr0.6TiO3Jie of ceramics sample The characteristic curve that electric constant and dielectric loss change with frequency；
Fig. 4 is comparative example and embodiment 1-5 addition Bi2O3-B2O3The Ba of-ZnO glass0.4Sr0.6TiO3The prestige of ceramics sample Boolean's scattergram；
Fig. 5 is comparative example and embodiment 1-5 addition Bi2O3-B2O3The Ba of-ZnO glass0.4Sr0.6TiO3The electricity of ceramics sample Hysteresis curves and dielectric constant, average disruptive field intensity and energy storage density with the variation diagram of glass addition, wherein (a) is electric hysteresis Loop line；B () is dielectric constant, average disruptive field intensity and energy storage density with the variation diagram of glass addition.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment is described in further detail to the present invention：
Comparative example
Ba of the present invention0.4Sr0.6TiO3The unleaded accumulation energy type ceramic dielectric material of base, its formula are (100-x) wt% Ba0.4Sr0.6TiO3+ xwt%Bi2O3-B2O3- ZnO, wherein x=0.
Step one：Prepare Ba0.4Sr0.6TiO3Powder is standby.According to mol ratio 0.6:1:0.4 weighs SrCO3、TiO2And BaCO3 It is mixed to form mixture.
Step 2：Mixture and zirconium ballstone and deionized water are taken, is 1 according to mass ratio:1:Ball is carried out successively after 1 mixing Mill, drying, after briquetting, be placed in batch-type furnace and 2 hours be incubated in 1150 DEG C, form the Ba of pure phase0.4Sr0.6TiO3Powder body, it is standby；
Step 3：By glass composite according to 60Bi2O3-30B2O3The mol ratio of -10ZnO (mol%) weighs raw material, in Pour into after stirring and evenly mixing is fully ground in mortar in corundum crucible, be placed in high temperature resistance furnace and heat.According to the intensification speed of setting Rate is warming up to 1300 DEG C, insulation 2h after, by wire drawing judge glass melt whether found well, without it was observed that bubble and Calculus, and high-temperature fusant has good ductility, shows that glass smelting is complete.Crucible can be taken out rapidly now and by high temperature melting Body is quickly poured on pre-heated copper coin.After vitreous humour just one-step forming, it is quickly placed to be warming up to 500 DEG C of annealing in advance The process of annealing 2h is carried out in stove, it is therefore intended that eliminate the residual stress in glass.Sample is taken out after furnace cooling, cut Process is cut, after sample is cut to the size of 10.0mm × 10.0mm × 2.0mm, prepares follow-up Crystallizing treatment.By the sample of well cutting Product place Muffle furnace in stove heat, rise to 700 DEG C with the heating rate of 10 DEG C/min, insulation 4h carry out Crystallizing treatment, treat with After stove cooling, that is, complete the preparation of sample.
Step 4：With pure phase Ba0.4Sr0.6TiO3, 0wt%Bi2O3-B2O3- ZnO, forms mixture, according to quality after mixing Percentage composition weighs to form full dispensing, standby；
Step 5：Full dispensing and zirconium ballstone and deionized water that step 4 is obtained are taken respectively, are 1 according to mass ratio:1:1 mixes Carry out ball milling, drying after conjunction successively, pelletize, sieve, form granulation material；
Step 6：Granulation material obtained by step 5 is made into sample under the pressure of 120MPa, then, is placed in and with zirconium oxide is In the aluminium oxide saggar of backing plate in high temperature box furnace, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, are heated up with 5 DEG C/min 2 hours are incubated to when 1350 DEG C, afterwards, are cooled to after 500 DEG C with 5 DEG C/min, are cooled to room temperature with the furnace；
Step 7：After the sample that polishing, cleaning step five are sintered, silver electrode slurry is uniformly coated in sample tow sides Material, sinters 20 minutes in 600 DEG C, obtains Ba0.4Sr0.6TiO3The unleaded accumulation energy type ceramic material sample of base.
Embodiment 1
Ba of the present invention0.4Sr0.6TiO3The unleaded accumulation energy type ceramic dielectric material of base, its formula are (100-x) wt% Ba0.4Sr0.6TiO3+ xwt%Bi2O3-B2O3- ZnO, wherein x=1.
Step one：Prepare Ba0.4Sr0.6TiO3Powder is standby.According to mol ratio 0.6:1:0.4 weighs SrCO3、TiO2And BaCO3 It is mixed to form mixture.
Step 2：Mixture and zirconium ballstone and deionized water are taken, is 1 according to mass ratio:1:Ball is carried out successively after 1 mixing Mill, drying, after briquetting, be placed in batch-type furnace and 2 hours be incubated in 1120 DEG C, form the Ba of pure phase0.4Sr0.6TiO3Powder body, it is standby；
Step 3：By glass composite according to 60Bi2O3-30B2O3The mol ratio of -10ZnO (mol%) weighs raw material, in Pour into after stirring and evenly mixing is fully ground in mortar in corundum crucible, be placed in high temperature resistance furnace and heat.According to the intensification speed of setting Rate is warming up to 1200 DEG C, after insulation 1.5h, judges whether glass melt is founded well by wire drawing, without it was observed that bubble And calculus, and high-temperature fusant has good ductility, shows that glass smelting is complete.Crucible can be taken out rapidly now and by high temperature Melt is quickly poured on pre-heated copper coin.After vitreous humour just one-step forming, it is quickly placed to be warming up in advance 500 DEG C and moves back The process of annealing 2h is carried out in stove, it is therefore intended that eliminate the residual stress in glass.Sample is taken out after furnace cooling, carried out Cutting process, prepares follow-up Crystallizing treatment after sample is cut to the size of 10.0mm × 10.0mm × 2.0mm.By well cutting With stove heat in sample placement Muffle furnace, 700 DEG C are risen to the heating rate of 10 DEG C/min, insulation 4h carries out Crystallizing treatment, treats After furnace cooling, that is, complete the preparation of sample.
Step 4：With pure phase 99wt%Ba0.4Sr0.6TiO3, 1wt%Bi2O3-B2O3- ZnO, forms mixture, presses after mixing Weigh to form full dispensing according to weight/mass percentage composition, it is standby；
Step 5：Full dispensing and zirconium ballstone and deionized water that step 4 is obtained are taken respectively, are 1 according to mass ratio:1:1 mixes Carry out ball milling, drying after conjunction successively, pelletize, sieve, form granulation material；
Step 6：Granulation material obtained by step 5 is made into sample under the pressure of 120MPa, then, is placed in and with zirconium oxide is In the aluminium oxide saggar of backing plate in high temperature box furnace, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, are heated up with 5 DEG C/min 2 hours are incubated to when 1250 DEG C, afterwards, are cooled to after 500 DEG C with 5 DEG C/min, are cooled to room temperature with the furnace；
Step 7：After the sample that polishing, cleaning step five are sintered, silver electrode slurry is uniformly coated in sample tow sides Material, sinters 20 minutes in 600 DEG C, obtains Ba0.4Sr0.6TiO3The unleaded accumulation energy type ceramic material sample of base.
Embodiment 2
Ba of the present invention0.4Sr0.6TiO3The unleaded accumulation energy type ceramic dielectric material of base, its formula are (100-x) wt% Ba0.4Sr0.6TiO3+ xwt%Bi2O3-B2O3- ZnO, wherein x=3.
Step one：Prepare Ba0.4Sr0.6TiO3Powder is standby.According to mol ratio 0.6:1:0.4 weighs SrCO3、TiO2And BaCO3 It is mixed to form mixture.
Step 2：Mixture and zirconium ballstone and deionized water are taken, is 1 according to mass ratio:1:Ball is carried out successively after 1 mixing Mill, drying, after briquetting, be placed in batch-type furnace and 1.5 hours be incubated in 1150 DEG C, form the Ba of pure phase0.4Sr0.6TiO3Powder body, it is standby With；
Step 3：By glass composite according to 60Bi2O3-30B2O3The mol ratio of -10ZnO (mol%) weighs raw material, in Pour into after stirring and evenly mixing is fully ground in mortar in corundum crucible, be placed in high temperature resistance furnace and heat.According to the intensification speed of setting Rate is warming up to 1250 DEG C, insulation 2h after, by wire drawing judge glass melt whether found well, without it was observed that bubble and Calculus, and high-temperature fusant has good ductility, shows that glass smelting is complete.Crucible can be taken out rapidly now and by high temperature melting Body is quickly poured on pre-heated copper coin.After vitreous humour just one-step forming, it is quickly placed to be warming up to 500 DEG C of annealing in advance The process of annealing 2h is carried out in stove, it is therefore intended that eliminate the residual stress in glass.Sample is taken out after furnace cooling, cut Process is cut, after sample is cut to the size of 10.0mm × 10.0mm × 2.0mm, prepares follow-up Crystallizing treatment.By the sample of well cutting Product place Muffle furnace in stove heat, rise to 750 DEG C with the heating rate of 10 DEG C/min, insulation 4h carry out Crystallizing treatment, treat with After stove cooling, that is, complete the preparation of sample.
Step 4：With pure phase 97wt%Ba0.4Sr0.6TiO3, 3wt%Bi2O3-B2O3- ZnO, forms mixture, presses after mixing Weigh to form full dispensing according to weight/mass percentage composition, it is standby；
Step 5：Full dispensing and zirconium ballstone and deionized water that step 4 is obtained are taken respectively, are 1 according to mass ratio:1:1 mixes Carry out ball milling, drying after conjunction successively, pelletize, sieve, form granulation material；
Step 6：Granulation material obtained by step 5 is made into sample under the pressure of 110MPa, then, is placed in and with zirconium oxide is In the aluminium oxide saggar of backing plate in high temperature box furnace, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, are heated up with 5 DEG C/min 3 hours are incubated to when 1280 DEG C, afterwards, are cooled to after 500 DEG C with 5 DEG C/min, are cooled to room temperature with the furnace；
Step 7：After the sample that polishing, cleaning step five are sintered, silver electrode slurry is uniformly coated in sample tow sides Material, sinters 20 minutes in 600 DEG C, obtains Ba0.4Sr0.6TiO3The unleaded accumulation energy type ceramic material sample of base.
Embodiment 3
Ba of the present invention0.4Sr0.6TiO3The unleaded accumulation energy type ceramic dielectric material of base, its formula are (100-x) wt% Ba0.4Sr0.6TiO3+ xwt%Bi2O3-B2O3- ZnO, wherein x=5.
Step one：Prepare Ba0.4Sr0.6TiO3Powder is standby.According to mol ratio 0.6:1:0.4 weighs SrCO3、TiO2And BaCO3 It is mixed to form mixture.
Step 2：Mixture and zirconium ballstone and deionized water are taken, is 1 according to mass ratio:1:Ball is carried out successively after 1 mixing Mill, drying, after briquetting, be placed in batch-type furnace and 2 hours be incubated in 1150 DEG C, form the Ba of pure phase0.4Sr0.6TiO3Powder body, it is standby；
Step 3：By glass composite according to 60Bi2O3-30B2O3The mol ratio of -10ZnO (mol%) weighs raw material, in Pour into after stirring and evenly mixing is fully ground in mortar in corundum crucible, be placed in high temperature resistance furnace and heat.According to the intensification speed of setting Rate is warming up to 1260 DEG C, after insulation 1.5h, judges whether glass melt is founded well by wire drawing, without it was observed that bubble And calculus, and high-temperature fusant has good ductility, shows that glass smelting is complete.Crucible can be taken out rapidly now and by high temperature Melt is quickly poured on pre-heated copper coin.After vitreous humour just one-step forming, it is quickly placed to be warming up in advance 500 DEG C and moves back The process of annealing 2h is carried out in stove, it is therefore intended that eliminate the residual stress in glass.Sample is taken out after furnace cooling, carried out Cutting process, prepares follow-up Crystallizing treatment after sample is cut to the size of 10.0mm × 10.0mm × 2.0mm.By well cutting With stove heat in sample placement Muffle furnace, 700 DEG C are risen to the heating rate of 10 DEG C/min, insulation 4h carries out Crystallizing treatment, treats After furnace cooling, that is, complete the preparation of sample.
Step 4：With pure phase 95wt%Ba0.4Sr0.6TiO3, 5wt%Bi2O3-B2O3- ZnO, forms mixture, presses after mixing Weigh to form full dispensing according to weight/mass percentage composition, it is standby；
Step 5：Full dispensing and zirconium ballstone and deionized water that step 4 is obtained are taken respectively, are 1 according to mass ratio:1:1 mixes Carry out ball milling, drying after conjunction successively, pelletize, sieve, form granulation material；
Step 6：Granulation material obtained by step 5 is made into sample under the pressure of 120MPa, then, is placed in and with zirconium oxide is In the aluminium oxide saggar of backing plate in high temperature box furnace, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, are heated up with 5 DEG C/min 2 hours are incubated to when 1290 DEG C, afterwards, are cooled to after 500 DEG C with 5 DEG C/min, are cooled to room temperature with the furnace；
Step 7：After the sample that polishing, cleaning step five are sintered, silver electrode slurry is uniformly coated in sample tow sides Material, sinters 30 minutes in 600 DEG C, obtains Ba0.4Sr0.6TiO3The unleaded accumulation energy type ceramic material sample of base.
Embodiment 4
Ba of the present invention0.4Sr0.6TiO3The unleaded accumulation energy type ceramic dielectric material of base, its formula are (100-x) wt% Ba0.4Sr0.6TiO3+ xwt%Bi2O3-B2O3- ZnO, wherein x=7.
Step one：Prepare Ba0.4Sr0.6TiO3Powder is standby.According to mol ratio 0.6:1:0.4 weighs SrCO3、TiO2And BaCO3 It is mixed to form mixture.
Step 2：Mixture and zirconium ballstone and deionized water are taken, is 1 according to mass ratio:1:Ball is carried out successively after 1 mixing Mill, drying, after briquetting, be placed in batch-type furnace and 1.5 hours be incubated in 1150 DEG C, form the Ba of pure phase0.4Sr0.6TiO3Powder body, it is standby With；
Step 3：By glass composite according to 60Bi2O3-30B2O3The mol ratio of -10ZnO (mol%) weighs raw material, in Pour into after stirring and evenly mixing is fully ground in mortar in corundum crucible, be placed in high temperature resistance furnace and heat.According to the intensification speed of setting Rate is warming up to 1280 DEG C, insulation 2h after, by wire drawing judge glass melt whether found well, without it was observed that bubble and Calculus, and high-temperature fusant has good ductility, shows that glass smelting is complete.Crucible can be taken out rapidly now and by high temperature melting Body is quickly poured on pre-heated copper coin.After vitreous humour just one-step forming, it is quickly placed to be warming up to 500 DEG C of annealing in advance The process of annealing 2h is carried out in stove, it is therefore intended that eliminate the residual stress in glass.Sample is taken out after furnace cooling, cut Process is cut, after sample is cut to the size of 10.0mm × 10.0mm × 2.0mm, prepares follow-up Crystallizing treatment.By the sample of well cutting Product place Muffle furnace in stove heat, rise to 750 DEG C with the heating rate of 10 DEG C/min, insulation 4h carry out Crystallizing treatment, treat with After stove cooling, that is, complete the preparation of sample.
Step 4：With pure phase 93wt%Ba0.4Sr0.6TiO3, 7wt%Bi2O3-B2O3- ZnO, forms mixture, presses after mixing Weigh to form full dispensing according to weight/mass percentage composition, it is standby；
Step 5：Full dispensing and zirconium ballstone and deionized water that step 4 is obtained are taken respectively, are 1 according to mass ratio:1:1 mixes Carry out ball milling, drying after conjunction successively, pelletize, sieve, form granulation material；
Step 6：Granulation material obtained by step 5 is made into sample under the pressure of 110MPa, then, is placed in and with zirconium oxide is In the aluminium oxide saggar of backing plate in high temperature box furnace, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, are heated up with 5 DEG C/min 2.5 hours are incubated to when 1300 DEG C, afterwards, are cooled to after 500 DEG C with 5 DEG C/min, are cooled to room temperature with the furnace；
Step 7：After the sample that polishing, cleaning step five are sintered, silver electrode slurry is uniformly coated in sample tow sides Material, sinters 20 minutes in 600 DEG C, obtains Ba0.4Sr0.6TiO3The unleaded accumulation energy type ceramic material sample of base.
Embodiment 5
Ba of the present invention0.4Sr0.6TiO3The unleaded accumulation energy type ceramic dielectric material of base, its formula are (100-x) wt% Ba0.4Sr0.6TiO3+ xwt%Bi2O3-B2O3- ZnO, wherein x=9.
Step one：Prepare Ba0.4Sr0.6TiO3Powder is standby.According to mol ratio 0.6:1:0.4 weighs SrCO3、TiO2And BaCO3 It is mixed to form mixture.
Step 2：Mixture and zirconium ballstone and deionized water are taken, is 1 according to mass ratio:1:Ball is carried out successively after 1 mixing Mill, drying, after briquetting, be placed in batch-type furnace and 2 hours be incubated in 1150 DEG C, form the Ba of pure phase0.4Sr0.6TiO3Powder body, it is standby；
Step 3：By glass composite according to 60Bi2O3-30B2O3The mol ratio of -10ZnO (mol%) weighs raw material, in Pour into after stirring and evenly mixing is fully ground in mortar in corundum crucible, be placed in high temperature resistance furnace and heat.According to the intensification speed of setting Rate is warming up to 1300 DEG C, after insulation 1.5h, judges whether glass melt is founded well by wire drawing, without it was observed that bubble And calculus, and high-temperature fusant has good ductility, shows that glass smelting is complete.Crucible can be taken out rapidly now and by high temperature Melt is quickly poured on pre-heated copper coin.After vitreous humour just one-step forming, it is quickly placed to be warming up in advance 500 DEG C and moves back The process of annealing 2h is carried out in stove, it is therefore intended that eliminate the residual stress in glass.Sample is taken out after furnace cooling, carried out Cutting process, prepares follow-up Crystallizing treatment after sample is cut to the size of 10.0mm × 10.0mm × 2.0mm.By well cutting With stove heat in sample placement Muffle furnace, 700 DEG C are risen to the heating rate of 10 DEG C/min, insulation 4h carries out Crystallizing treatment, treats After furnace cooling, that is, complete the preparation of sample.
Step 4：With pure phase 91wt%Ba0.4Sr0.6TiO3, 9wt%Bi2O3-B2O3- ZnO, forms mixture, presses after mixing Weigh to form full dispensing according to weight/mass percentage composition, it is standby；
Step 5：Full dispensing and zirconium ballstone and deionized water that step 4 is obtained are taken respectively, are 1 according to mass ratio:1:1 mixes Carry out ball milling, drying after conjunction successively, pelletize, sieve, form granulation material；
Step 6：Granulation material obtained by step 5 is made into sample under the pressure of 120MPa, then, is placed in and with zirconium oxide is In the aluminium oxide saggar of backing plate in high temperature box furnace, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, are heated up with 5 DEG C/min 3 hours are incubated to when 1350 DEG C, afterwards, are cooled to after 500 DEG C with 5 DEG C/min, are cooled to room temperature with the furnace；
Step 7：After the sample that polishing, cleaning step five are sintered, silver electrode slurry is uniformly coated in sample tow sides Material, sinters 25 minutes in 600 DEG C, obtains Ba0.4Sr0.6TiO3The unleaded accumulation energy type ceramic material sample of base.

Claims (9)

1. a kind of Bi2O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic, it is characterised in that formula is (100-x) Ba0.4Sr0.6TiO3+x Bi2O3-B2O3- ZnO, wherein x=1～9wt%, x are mass percent.
2. a kind of Bi according to claim 12O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic, which is special Levy and be, x=1wt%, 3wt%, 5wt%, 7wt% or 9wt%.
3. a kind of Bi2O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3The preparation method of base energy storage ceramic, it is characterised in that bag Include following steps：
Step one：According to mol ratio 0.6:1:0.4 weighs SrCO3、TiO2And BaCO3It is mixed to form mixture A；Mixture A is entered Row ball milling, drying, after briquetting, 1.5～2 hours are incubated in 1120～1150 DEG C, form the Ba of pure phase0.4Sr0.6TiO3Powder body, it is standby With；
Step 2：According to Bi2O3：B2O3：ZnO=6:3:1 mol ratio weighs raw material, is fully ground stirring and evenly mixing post-heating, rises Temperature is incubated 1.5～2h to after 1200～1300 DEG C and obtains high-temperature fusant, then by high-temperature fusant first one-step forming, after just one-step forming Made annealing treatment, cut after annealing, the sample of well cutting is carried out into Crystallizing treatment, Bi after cooling, is obtained2O3-B2O3-ZnO Glass dust；
Step 3：By the Ba for obtaining0.4Sr0.6TiO3Powder body and Bi2O3-B2O3- ZnO glass dust is according to (100-x) Ba0.4Sr0.6TiO3+xBi2O3-B2O3- ZnO is mixed to get mixture B, take after mixture B is mixed with zirconium ballstone and deionized water according to It is secondary to carry out ball milling, drying, pelletize, sieve, granulation material is formed, wherein x=1～9wt%, x are mass percent；
Step 4：Granulation material obtained by step 3 is made into sample under the pressure of 110～120MPa, is then heated up with 2 DEG C/min To 500 DEG C of insulation 60min, be incubated 2～3 hours when 1250～1350 DEG C are warming up to 5 DEG C/min, afterwards, lowered the temperature with 5 DEG C/min To after 500 DEG C, room temperature is cooled to the furnace；
Step 5：After the sample that polishing, cleaning step four are sintered, silver electrode paste is uniformly coated in sample tow sides, in 600 DEG C sinter 20～30 minutes, obtain Bi2O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic.
4. a kind of Bi according to claim 32O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3The preparation of base energy storage ceramic Method, it is characterised in that annealing is specially in step 2：Anneal in 500 DEG C of annealing furnace is warming up in advance 2h；Annealing The size of 10.0mm × 10.0mm × 2.0mm is cut to afterwards.
5. a kind of Bi according to claim 32O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3The preparation of base energy storage ceramic Method, it is characterised in that Crystallizing treatment is specially in step 2：The sample of well cutting is placed on stove heat in Muffle furnace, 4h is incubated after 700 DEG C～750 are risen to the heating rate of 10 DEG C/min.
6. a kind of Bi according to claim 32O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3The preparation of base energy storage ceramic Method, it is characterised in that step one, Ball-milling Time is 4～6 hours in three.
7. a kind of Bi according to claim 32O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3The preparation of base energy storage ceramic Method, it is characterised in that take in step 3 carried out after mixture B is mixed with zirconium ballstone and deionized water successively ball milling, drying after Drying material is obtained, binding agent is added into drying material carries out pelletize, binding agent accounts for 8～10%, Ran Houfen of drying material quality Do not cross 40 mesh and 80 mesh sieves take middle material and obtain granulation material.
8. a kind of Bi according to claim 72O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3The preparation of base energy storage ceramic Method, it is characterised in that described adhesive is polyvinyl alcohol water solution.
9. a kind of Bi according to claim 72O3-B2O3- ZnO glass adds Ba0.4Sr0.6TiO3The preparation of base energy storage ceramic Method, it is characterised in that the mass concentration of binding agent is 4～6%.
CN201610905905.2A 2016-10-18 2016-10-18 A kind of Bi2O3‑B2O3ZnO glass adds Ba0.4Sr0.6TiO3Base energy storage ceramic and preparation method thereof Pending CN106542821A (en)

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Application publication date: 20170329